Epichlorohydrin, manufacturing process and use

ABSTRACT

A method for the manufacture of a material selected from epoxy resins, glycidyl esters, glycidyl ethers, glycidyl amides, glycidyl imides, epichlorohydrin elastomers, coagulants, wet-strength resins, cationization agents, flame retardants and detergent ingredients by subjecting a product containing epichlorohydrin and trichloropropane to a reaction in order to obtain the material, wherein the product contains a positive amount of trichloropropane in an amount of up to less than 0.01 g of trichloropropane per kg of product.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present patent application is a division of U.S. application Ser.No. 12/663,749, filed Dec. 9, 2009, now allowed; which is a U.S.national stage application under 35 U.S.C. §371 of InternationalApplication No. PCT/EP2008/057247 filed Jun. 11, 2008, which claims thebenefit of French Patent application Nos. FR 07/55696 filed on Jun. 12,2007 and FR 07/57751 filed Sep. 21, 2007, which claims the benefit ofU.S. Provisional application No. 61/013,672 filed Dec. 14, 2007 and ofU.S. Provisional application No. 61/007,661 filed Dec. 14, 2007, thecontent of all of these applications being incorporated herein byreference for all purposes.

The present invention relates to an epichlorohydrin-based product, to aprocess for the manufacture and purification thereof and to the use ofthe product in various manufactures.

Epichlorohydrin is a reaction intermediate in the manufacture of epoxyresins, synthetic elastomeres, glycidyl ethers, polyamide resins, etc.(Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol. A9,p. 539). The epichlorohydrin can be manufactured, for instance, bydehydrochlorination of dichloropropanol derived from hypochlorination ofallyl chloride. The epichlorohydrin thus obtained is not suitable forcertain applications.

The object of the present invention is to provide a product containingepichlorohydrin which does not have these disadvantages.

The invention hence relates to a product containing epichlorohydrin andtrichloropropane, wherein the amount of trichloropropane is of less than0.01 g of trichloropropane per kg of product.

One of the essential characteristics of the invention resides in the lowamount of trichloropropane present in the epichlorohydrin product. Thepresence of trichloropropane amongst other halogenated hydrocarbons inepichlorohydrin have indeed proven troublesome in some of theapplications, such as for example, in manufacturing epoxy resinsintended for the electrical component and printed circuit industry. Somehalogenated hydrocarbons, among which trichloropropane, for instance areor are suspected to be carcinogenic, are suspected to have developmenttoxicity, reproductive toxicity, cardiologic toxicity, endocrinetoxicity, immunotoxicity and toxicity to the liver, the kidneys, thenerves, the respiratory tract and to the skin. They can remain in thefinal products and possibly degrade with a concomitant deterioration ofthe properties of the final products. They can exhibit or degrade incompounds exhibiting some toxicity leading to safety issues especiallywhen the final products are intended to be in contact with food anddrink. Moreover, they can accumulate in and contaminate industrialwaters such as wastewaters for instance or water containing pulp that isrecycled in the pulp and paper industry. In the latter case, theirhigher concentration can increase contamination of the paper made usingthe recycled water.

The epichlorohydrin content in the product is generally greater than 900g of epichlorohydrin per kg of product, preferably at least 950 g/kg,more preferably at least 990 g/kg and most particularly preferably atleast 999 g/kg.

The trichloropropane in the product according to the invention ispresent, in an amount of generally less than or equal to 0.008 g/kg ofproduct, often of less than or equal to 0.006 g/kg, frequently of lessthan or equal to 0.004 g/kg, commonly of less than or equal to 0.002g/kg, in many cases of less than or equal to 0.001 g/kg, andparticularly of less than or equal to 0.0005 g/kg. That content isusually of at least 0.001 mg/kg.

The trichloropropane may be selected from any isomer oftrichloropropane, alone or in combination, and the content of TCPa inthe product according to the invention refers to the sum of all theisomers.

The trichloropropane can be selected from 1,2,3-trichloropropane,1,1,1-trichloropropane, 1,1,3-trichloropropane, 1,1,2-trichloropropaneand any mixtures of at least two of them. The trichloropropane is often1,1,1-trichloropropane.

The product according to the invention may contain in addition totrichloropropane and epichlorohydrin, at least one halogenatedhydrocarbon different from trichloropropane. That halogenatedhydrocarbon can be chosen from chloropropene, trichloropropene,chloropropanol, chloropropenol, dichloropropene, dichloropropane,dichloropropanol, monochloropropanediol, chloroethers,monochlorobenzene, and any mixture of at least two of them.

The content of that halogenated hydrocarbon in the product is usually ofless than 1 g/kg of product, commonly less than or equal to 0.8 g/kg ofproduct, usually less than or equal to 0.6 g/kg, in many cases less thanor equal to 0.5 g/kg, often less than or equal to 0.4 g/kg, frequentlyless than or equal to 0.2 g/kg, more often less than or equal to 0.1g/kg, more frequently less than or equal to 0.05 g/kg, in particularless than or equal to 0.01 g/kg, and specifically less than or equal to0.001 g/kg. This content is generally greater than or equal to 0.001mg/kg.

The halogenated hydrocarbon may be an aliphatic or an aromatichalogenated hydrocarbon, optionally containing oxygen, preferably analiphatic halogenated hydrocarbon, such as:

-   -   chloropropene, often 2-chloro-1-propene, frequently        1-chloro-1-propene cis, usually 1-chloro-1-propene trans,        specifically 3-chloro-1-propene, and any mixture of at least two        of them    -   chloropropane, often 2-chloropropane, frequently        1-chloropropane, and any mixture of at least two of them    -   chloromethane, often dichloromethane, frequently        trichloromethane, usually tetrachloromethane, and any mixture of        at least two of them    -   dichloroethane, often 1,2-dichloroethane,    -   chloroethanol, often 2-chloroethanol,    -   trichloropropene, often 1,3,3-trichloro-1-propene-cis,        frequently 1,3,3-trichloro-1-propene-trans, usually        1,2,3-trichloropropene-cis, specifically        1,2,3-trichloropropene-trans, and any mixture of at least two of        them    -   chloropropanol, often 3-chloro-1-propanol,    -   chloropropenol, often 2-chloro-2-propen-1-ol, frequently        3-chloro-2-propene-1-ol cis and specifically        3-chloro-2-propene-1-ol trans, and any mixture of at least two        of them    -   dichloropropene, often cis-1,3-dichloropropene, frequently        trans-1,3-dichloropropene, usually 3,3-dichloro-1-propene,        frequently 2,3-dichloro-1-propene, usually        1,3-dichloro-1-propene-cis, specifically        1,3-dichloro-1-propene-trans, and any mixture of at least two of        them,    -   dichloropropane, preferably 1,3-dichloropropane,        1,2-dichloropropane, 2,2-dichloropropane, and any mixture        thereof    -   dichloropropanol, often 1,3-dichloropropan-2-ol,        2,3-dichloropropan-1-ol, and mixtures thereof,    -   monochloropropanediol, often 3-chloro-1,2-propanediol,        frequently 2-chloro-1,3-propanediol, and mixtures thereof, and    -   chloroethers, preferably chosen from chloroethers of crude        formula: C₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂, and        mixtures of at least two of them,    -   of crude formula C₄H₇ClO₂, C₆H₉Cl₃, C₆H₉Cl₃O₂, C₉H₁₇Cl₃O₄,        C₉H₁₅Cl₅O, C₃H₃Cl₃, and mixtures of at least two of them    -   dichloroepoxypropane.

Haloketones and epichlorohydrin are not considered to be halogenatedhydrocarbons.

Aromatic halogenated hydrocarbons comprise at least one ring of aromaticnature and a halogen atom. The halogen atom is preferably directlyattached to the aromatic ring. The halogen may be chosen from fluorine,chlorine, bromine, iodine and mixtures thereof. Chlorine is preferred.The aromatic ring may be mononuclear or polynuclear, and is preferablymononuclear. The aromatic halogenated hydrocarbons may be chosen frommono-, di-, tri-, tetra-, penta- and hexachloro-benzenes and/ornaphthalenes. Monochlorobenzene is particularly preferred.

Without wishing to be tied to one theoretical explanation, it isbelieved that monochlorobenzene may come from the process formanufacturing epichlorohydrin, in particular when this is obtained bydehydrochlorination of dichloropropanol. More specifically, it isbelieved that monochlorobenzene may be present in the dichloropropanol,in particular when this is obtained by a process for chlorinatingglycerol using a chlorinating agent containing hydrogen chloride. Morespecifically still, it is believed that chlorobenzene may be present inthe hydrogen chloride, in particular when this comes from anothermanufacturing process, such as the manufacture of isocyanates,diisocyanates or polyisocyanates, such as for example4,4-methylenediphenyl diisocyanate (MDI) or toluene diisocyanate (TDI)or hexamethylene-1,6-diisocyanate (HDI).

The product according to the invention can contain chloropropene, in acontent usually less than or equal to 0.8 g/kg of product, generallyless than or equal to 0.6 g/kg, in many cases less than or equal to 0.5g/kg, often less than or equal to 0.4 g/kg, commonly less than or equalto 0.2 g/kg, advantageously less than or equal to 0.1 g/kg, particularlyless than or equal to 0.05 g/kg, specifically less than or equal to 0.01g/kg. Values less than or equal to 0.001 g/kg give good results. Thatcontent is usually of at least 0.001 mg/kg. The chloropropene may beselected from 2-chloro-1-propene, 1-chloro-1-propene cis,1-chloro-1-propene trans, 3-chloro-1-propene, and any mixture of atleast two of them.

The product according to the invention can contain trichloropropene, inan amount a content usually less than or equal to 0.8 g/kg of product,generally less than or equal to 0.6 g/kg, commonly less than or equal to0.5 g/kg, in many cases less than or equal to 0.4 g/kg, often less thanor equal to 0.2 g/kg, frequently less than or equal to 0.1 g/kg,particularly less than or equal to 0.05 g/kg, specifically less than orequal to 0.01 g/kg. A content of less than or equal to 0.001 g/kg givesgood results. That content is usually of at least 0.001 mg/kg. Thetrichloropropene may be selected from 1,3,3-trichloro-1-propene-cis,1,3,3-trichloro-1-propene-trans, 1,2,3-trichloropropene-cis,specifically 1,2,3-trichloropropene-trans and any mixtures of at leasttwo of them.

The product according to the invention can contain chloropropenol, in acontent usually less than or equal to 0.8 g/kg of product, generallyless than or equal to 0.6 g/kg, in many cases less than or equal to 0.5g/kg, often less than or equal to 0.4 g/kg, commonly less than or equalto 0.2 g/kg, advantageously less than or equal to 0.1 g/kg, particularlyless than or equal to 0.05 g/kg, specifically less than or equal to 0.01g/kg. Values less than or equal to 0.001 g/kg give good results. Thatcontent is usually of at least 0.001 mg/kg. The chloropropenol may beselected from 2-chloro-2-propen-1-ol, 3-chloro-2-propene-1-ol cis,3-chloro-2-propene-1-ol trans and any mixtures of at least two of them.

The product according to the invention may contain dichloropropene, in acontent a content usually less than or equal to 0.8 g/kg of product,generally less than or equal to 0.6 g/kg, in many cases less than orequal to 0.5 g/kg, often less than or equal to 0.4 g/kg, commonly lessthan or equal to 0.2 g/kg, advantageously less than or equal to 0.1g/kg, particularly less than or equal to 0.05 g/kg, specifically lessthan or equal to 0.01 g/kg. Values less than or equal to 0.001 g/kg givegood results. That content is usually of at least 0.001 mg/kg. Thedichloropropene may be selected from 3,3-dichloro-1-propene,2,3-dichloro-1-propene, 1,3-dichloro-1-propene-cis,1,3-dichloro-1-propene-trans, and any mixtures of at least two of them.

The product according to the invention can contain dichloropropane, in acontent usually less than or equal to 0.8 g/kg of product, generallyless than or equal to 0.6 g/kg, in many cases less than or equal to 0.5g/kg, often less than or equal to 0.4 g/kg, commonly less than or equalto 0.2 g/kg, advantageously less than or equal to 0.1 g/kg, particularlyless than or equal to 0.05 g/kg, specifically less than or equal to 0.01g/kg. Values less than or equal to 0.001 g/kg give good results. Thatcontent is usually of at least 0.001 mg/kg. The dichloropropane may beselected from 1,3-dichloropropane, 1,2-dichloropropane,2,2-dichloropropane, and any mixture of at least two of them.

The product according to the invention can contain dichloropropanol, ina content usually less than or equal to 0.8 g/kg of product, generallyless than or equal to 0.6 g/kg, in many cases less than or equal to 0.5g/kg, often less than or equal to 0.4 g/kg, commonly less than or equalto 0.2 g/kg, advantageously less than or equal to 0.1 g/kg, particularlyless than or equal to 0.05 g/kg, specifically less than or equal to 0.01g/kg. Values less than or equal to 0.001 g/kg give good results. Thatcontent is usually of at least 0.001 mg/kg. The dichloropropanol may beselected from 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and anymixtures thereof.

The product according to the invention can containmonochloropropanediol, in a content usually less than or equal to 0.8g/kg of product, generally less than or equal to 0.6 g/kg, in many casesless than or equal to 0.5 g/kg, often less than or equal to 0.4 g/kg,commonly less than or equal to 0.2 g/kg, advantageously less than orequal to 0.1 g/kg, particularly less than or equal to 0.05 g/kg,specifically less than or equal to 0.01 g/kg. Values less than or equalto 0.001 g/kg give good results. That content is usually of at least0.001 mg/kg. The monochloropropanediol may be selected from3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and any mixturesthereof.

The product according to the invention usually can contain chloroethersin in a content usually less than or equal to 0.8 g/kg of product,generally less than or equal to 0.6 g/kg, in many cases less than orequal to 0.5 g/kg, often less than or equal to 0.4 g/kg, commonly lessthan or equal to 0.2 g/kg, advantageously less than or equal to 0.1g/kg, particularly less than or equal to 0.05 g/kg, specifically lessthan or equal to 0.01 g/kg. Values less than or equal to 0.001 g/kg givegood results. That content is usually of at least 0.001 mg/kg. Thechloroethers may be selected from chloroethers of crude formulaC₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂, and any mixtures thereof.

The product according to the invention usually contains chlorobenzene,often monochlorobenzene, in an amount in a content usually less than orequal to 0.8 g/kg of product, generally less than or equal to 0.6 g/kg,in many cases less than or equal to 0.5 g/kg, often less than or equalto 0.4 g/kg, commonly less than or equal to 0.2 g/kg, advantageouslyless than or equal to 0.1 g/kg, particularly less than or equal to 0.05g/kg, specifically less than or equal to 0.01 g/kg. Values less than orequal to 0.001 g/kg give good results. That content is usually of atleast 0.001 mg/kg.

The product according to the invention may also contain in addition,compounds which are not halogenated hydrocarbons such as defined above,such as for example:

-   -   aldehydes, like acetaldehyde, acrolein, isobutanal, isopentanal    -   alkyl glycidyl ether, like methyl glycidyl ether,    -   ketones, like acetone, chloroacetone, cyclopentanone,        2-butanone, cyclohexanone, 2-methyl-2-cyclopentene-1-one,        3,5-dimethyl-2-cyclohexene-1-one ketone of crude formula C₅H₁₀O,        C₆H₁₂O,    -   aliphatic alcohols, like isopropanol, allyl alcohol, glycerol,    -   aromatic alcohols like phenol    -   hydroxyketones like hydroxyacetone and    -   epoxides different from epichlorohydrin, like propylene oxide,        1,2-epoxyhexane, glycidol,    -   hydrocarbons like methylcyclopentane, ethylbenzene,    -   compounds of crude formula C₆H₁₀O, C₇H₁₀O, C₇H₁₄O₂, C₆H₈O₂,        C₉H₁₀O₂.

The product according to the invention can contain at least onealdehyde, in a content usually less than or equal to 0.8 g/kg ofproduct, generally less than or equal to 0.6 g/kg, in many cases lessthan or equal to 0.5 g/kg, often less than or equal to 0.4 g/kg,commonly less than or equal to 0.2 g/kg, advantageously less than orequal to 0.1 g/kg, particularly less than or equal to 0.05 g/kg,specifically less than or equal to 0.01 g/kg. Values less than or equalto 0.001 g/kg give good results. That content is usually of at least0.001 mg/kg. The aldehyde may be selected from acetaldehyde, acrolein,isobutanal, isopentanal and any mixtures of at least two of them.

The product according to the invention can contain acrolein in an amountusually of less than 0.07 g/kg of product, generally at most 0.01 g/kgcommonly at most 0.005 g/kg. This content is usually at least 0.001g/kg.

The product according to the invention can contain at least one alkylglycidyl ether, in a content usually less than or equal to 0.8 g/kg ofproduct, generally less than or equal to 0.6 g/kg, in many cases lessthan or equal to 0.5 g/kg, often less than or equal to 0.4 g/kg,commonly less than or equal to 0.2 g/kg, advantageously less than orequal to 0.1 g/kg, particularly less than or equal to 0.05 g/kg,specifically less than or equal to 0.01 g/kg. Values less than or equalto 0.001 g/kg give good results. That content is usually of at least0.001 mg/kg. The alkyl glycidyl ether may be selected from methyl-,ethyl-, propyl-, butyl glycidyl ethers, and any mixtures of at least twoof them.

The product according to the invention can contain methyl glycidyl etherin an amount usually of at most 0.5 g/kg of product, generally at most0.1 g/kg and commonly at most 0.05 g/kg. This content is usually of atleast 0.001 g/kg.

The product according to the invention can contain ketones, in a contentusually less than or equal to 0.8 g/kg of product, generally less thanor equal to 0.6 g/kg, in many cases less than or equal to 0.5 g/kg,often less than or equal to 0.4 g/kg, commonly less than or equal to 0.2g/kg, advantageously less than or equal to 0.1 g/kg, particularly lessthan or equal to 0.05 g/kg, specifically less than or equal to 0.01g/kg. Values less than or equal to 0.001 g/kg give good results. Thatcontent is usually of at least 0.001 mg/kg. The ketones may be selectedfrom acetone, chloroacetone, 2-butanone, cyclopentanone, cyclohexanone,2-methyl-2-cyclopentene-1-one, 3,5-dimethyl-2-cyclohexene-1-one, ketonesof crude formula C₅H₁₀O, C₆H₁₂O, and any mixtures of at least two ofthem.

The product according to the invention can contain cyclopentanone in anamount usually higher than or equal to 0.001 mg/kg, generally higherthan or equal to 0.01 mg/kg, commonly higher than or equal to 0.1 mg/kgand in many cases higher than or equal to 0.001 g/kg. That content isusually lower than or equal to 0.5 g/kg, generally lower than or equalto 0.3 g/kg, commonly lower than or equal to 0.1 g/kg, in many caseslower than or equal to 0.05 g/kg, often lower than or equal to 0.01 g/kgand particularly lower than or equal to 0.005 g/kg. That content isusually higher than or equal to 0.001 mg/kg, generally higher than orequal to 0.01 mg/kg, commonly higher than or equal to 0.1 mg/kg, in manycases higher than or equal to 0.5 mg/kg and in particular higher than orequal to 1 mg/kg

The product according to the invention can contain chloroacetone in anamount usually of less than 0.05 g/kg of product, generally at most 0.03g/kg and commonly at most 0.01 g/kg. This content is usually at least0.001 g/kg

The product according to the invention can contain aliphatic alcohols,in a content usually less than or equal to 0.8 g/kg of product,generally less than or equal to 0.6 g/kg, in many cases less than orequal to 0.5 g/kg, often less than or equal to 0.4 g/kg, commonly lessthan or equal to 0.2 g/kg, advantageously less than or equal to 0.1g/kg, particularly less than or equal to 0.05 g/kg, specifically lessthan or equal to 0.01 g/kg. Values less than or equal to 0.001 g/kg givegood results. That content is usually of at least 0.001 mg/kg. Thealiphatic alcohols may be selected from isopropanol, allyl alcohol,glycerol, and any mixtures of at least two of them.

The product according to the invention can contain hydroxyketones, in acontent in a content usually less than or equal to 0.8 g/kg of product,generally less than or equal to 0.6 g/kg, in many cases less than orequal to 0.5 g/kg, often less than or equal to 0.4 g/kg, commonly lessthan or equal to 0.2 g/kg, advantageously less than or equal to 0.1g/kg, particularly less than or equal to 0.05 g/kg, specifically lessthan or equal to 0.01 g/kg. Values less than or equal to 0.001 g/kg givegood results. That content is usually of at least 0.001 mg/kg. Thehydroxyketone is often hydroxyacetone.

The product according to the invention can contain epoxides differentfrom epichlorohydrin, in a content usually less than or equal to 0.8g/kg of product, generally less than or equal to 0.6 g/kg, in many casesless than or equal to 0.5 g/kg, often less than or equal to 0.4 g/kg,commonly less than or equal to 0.2 g/kg, advantageously less than orequal to 0.1 g/kg, particularly less than or equal to 0.05 g/kg,specifically less than or equal to 0.01 g/kg. Values less than or equalto 0.001 g/kg give good results. That content is usually of at least0.001 mg/kg. The epoxide may be selected from propylene oxide,1,2-epoxy-hexane, glycidol, and any mixtures of at least two of them.

The product according to the invention can contain glycidol in an amountusually of at most 0.5 g/kg of product, generally of at most 0.2 g/kg,frequently of at most 0.10 g/kg of product, commonly of at most 0.05g/kg of product, often of at most 0.01 g/kg and frequently of at most0.005 g/kg.

The product according to the invention usually contains glycerol,hydroxyacetone and glycidol, of which the sum of the contents is usuallyless than 0.1 g/kg of product, commonly at most 0.01 g/kg and generallyat most 0.005 g/kg. This content is usually at least 0.001 g/kg.

The invention also relates to a process for manufacturing a productcontaining epichlorohydrin, wherein the amount of trichloropropane is ofless than 0.01 g of trichloropropane per kg of product, comprising thefollowing steps:

-   a) in a liquid reaction medium, a mixture of dichloropropanol    containing 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol, in    which the 1,3-dichloro-2-propanol content is at least 10 wt %, is    reacted with at least one basic compound in order to form    epichlorohydrin and at least one salt; and-   b) at least one part of the liquid reaction medium from step a) is    subjected to a settling operation in which a first fraction    containing most of the epichlorohydrin which was contained in the    part of the reaction medium from step a) before the settling    operation is separated from a second fraction containing most of the    salt which was contained in the part of the reaction medium from    step a) before the settling operation; and-   c) the first fraction separated in step b) is subjected to at least    one supplementary treatment chosen from dilution, concentration,    evaporation, distillation, stripping, liquid/liquid extraction and    adsorption operations, alone or in combination.

In the rest of the document the expression “dichloropropanol” will beused to denote the dichloropropanol mixture.

The expression “most of” is understood to mean “half and more than halfof”, i.e. 50% by weight or more than 50% by weight.

The halogenated hydrocarbons may especially be produced during thevarious steps of the dichloropropanol manufacturing process.

The dichloropropanol from step a) of the process according to theinvention may be produced, for example, by chlorination of glyceroland/or by hypochlorination of allyl chloride, the allyl chloride beingitself produced by chlorination of propylene. The glycerol may beobtained from oil or grease of plant or animal origin. Oil-producingplant or crops are for example corn, cashew nut, oat, palm, lupine,rubber seed, kenaf, calendula, cotton, hemp, soybean, coffee, linseed,hazelnut, euphorbia, pumpkin seed, coriander, mustard, camelina, sesame,crambe, safflower, buffalo gourd, rice, tung oil tree, sunflower, cocoa,peanut, opium poppy, rapeseed, olive tree, piassaya, gopher plant,castor bean, bacuri, pecan, jojoba, babassu palm, jatropha, e.g.jatropha Curcas L., Chinese tallow or Tridica Sebifera L., macadamianut, brazil nut, avocado, coconut, oiticia, buriti palm, pequi, macaubapalm and oil palm. Oil-producing algae are for example Neochlorisoleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylumtricomutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmis chui,Tetraselmis suecica, Isochrysis galbana, Nannochloropsis salina,Nannochloris atomus Butcher, Nannochloris maculata Butcher,Nannochloropsis gaditana Lubian, and Nannochloropsis oculata, Algalstrains such as Botryococcus braunii, Botryococcus, Dunaliellatertiolecta, Nannochloris sp., Spirulina species, Chlorophyceae (greenalgae) and Bacilliarophy (diatom algae). Methyl glycidyl ether may comefrom glycerol methyl ethers which are impurities of a glycerol obtainedby transesterification of fats or oils of animal or vegetable origin, asdescribed in Patent Applications FR 06/05325 and FR 07/53863 filed inthe name of Solvay SA, the contents of which are incorporated herein byreference. The haloketones such as, for example, chloroacetone may begenerated in the dichloropropanol manufacturing process by chlorinationof glycerol and/or during step a) of the process according to theinvention.

Steps a) and b) of the process used to manufacture the product accordingto the invention may be carried out under conditions such as thosedescribed in Applications FR 07/53375 and FR 07/55448 filed in the nameof Solvay SA. The liquid reaction medium from step a) may especiallycontain an organic solvent, such as trichloropropane for example.

The dichloropropanol used in step a) can be fed to step a) as an aqueouscomposition, as an organic composition or a mixture thereof.

The dichloropropanol content of the aqueous composition is usuallyhigher than or equal to 1 g/kg, often higher than or equal to 10 g/kg,frequently higher than or equal to 50 g/kg and particularly higher thanor equal to 90 g/kg. That content is generally lower than or equal to500 g/kg, usually lower than or equal to 200 g/kg, often lower than orequal to 150 g/kg, frequently lower than or equal to 120 g/kg andparticularly lower than or equal to 110 g/kg. A content of 100 g/kg isconvenient.

The dichloropropanol content of the organic composition is usuallyhigher than or equal to 500 g/kg, often higher than or equal to 750g/kg, frequently higher than or equal to 800 g/kg and particularlyhigher than or equal to 850 g/kg. that content is usually lower than orequal to 999 g/kg, often lower than or equal to 950 g/kg, frequentlylower than or equal to 900 g/kg and particularly lower than or equal to880 g/kg. A content of 870 g/kg is convenient.

In a particular embodiment, the mixture of dichloropropanol used in stepa) of the process according to the invention can contain at least onechloro alkoxy propanol, as described in USP 61/007,661 of SOLVAY SA. Thecontent of chloro alkoxy propanol in the dichloropropanol is usuallylower than or equal to 0.2 g/kg, generally lower than or equal to 0.1g/kg, often lower than or equal to 0.06 g/kg and frequently lower thanor equal to 0.04 g/kg. This content is usually higher than or equal to0.001 g/kg.

The chloro alkoxy propanol is often a chloro methoxy propanol. Thechloro methoxy propanol can be selected from2-chloro-3-methoxy-1-propanol, 1-chloro-3-methoxy-2-propanol,3-chloro-2-methoxy-1-propanol, and any mixture of at least two of them.

Steps a) to c) of the process for obtaining the product according to theinvention may independently be carried out in continuous or batch mode.It is preferred to carry out steps a) to c) in continuous mode.

In the process according to the invention, the reaction from step a) maybe carried out in one or more reaction zones, preferably in at least tworeaction zones, more preferably in at least three reaction zones andmore particularly preferably at least four reaction zones. The reactionzones may be composed of volumes assembled in a single jacket or volumesin separate jackets. In the case where the volumes are assembled in asingle jacket, the reaction zones may be positioned horizontally orvertically with respect to one another. In the case where the zones arepositioned horizontally with respect to one another, the transfer fromone zone to another may take place by gravity or by forced circulation.In the case of circulation by gravity, the transfer may be carried outwith or without settling in one or in several channels. Transfer in asingle channel without settling is preferred. In the case where thezones are assembled vertically, the transfer from one zone to anothermay take place by gravity or by forced circulation. Transfer by gravityis preferred. The implementation of step a) in a mechanically stirredcolumn that is subdivided by perforated dividing plates is particularlypreferred. The stirring may be carried out by any known means, forexample by rotation of a spindle in the liquid medium or by pulsing ofthe flow. Columns stirred by rotation of a spindle are particularlypreferred. These reaction zones may be placed in any configuration, inseries, in parallel or some in series and others in parallel.

In the process according to the invention, the reaction zones may besupplied independently of one another with dichloropropanol, with thebasic compound, with water or with at least two of these compounds. Whenseveral reaction zones are in series, it is preferred to supply themajor part of the basic compound to the first reaction zone of theseries.

The expression “reaction zones” is understood to mean zones where allthe compounds needed for the reaction from step a) are found, namelydichloropropanol, the basic compound and an optional reaction solvent.

In the process for manufacturing the epichlorohydrin-based productaccording to the invention, the dichloropropanol may be dichoropropanolextrinsic to the process according to the invention, recycleddichloropropanol or a mixture of the two, such as has been definedbefore in Applications FR 07/53375 and FR 07/55448 filed in the name ofSolvay SA. The expression “recycled dichloropropanol” is understood tomean dichloropropanol which has been separated in a step subsequent tostep b) in the process according to the invention and which has thenbeen recycled to step a) of said process. The term “extrinsicdichloropropanol” is understood to mean dichloropropanol which has notbeen recycled in the process according to the invention.

The temperature, pressure, reaction time and residence time may havedifferent values in the various reaction zones, such as defined inapplications FR 07/53375 and FR 07/55448 filed in the name of Solvay SA.

The ratio of the 2,3-dichloro-1-propanol content to the1,3-dichloro-2-propanol content in the dichloropropanol may be differentdepending on the reaction zone to which the dichloropropanol issupplied. This ratio may be such as described in applications FR07/53375 and FR 07/55448 filed in the name of Solvay SA.

The molar ratio of dichloropropanol to the basic compound may bedifferent depending on the reaction zone to which these compounds aresupplied. This ratio may be such as described in applications FR07/53375 and FR 07/55448 filed in the name of Solvay SA.

The basic compound may be an organic or inorganic basic compound.Organic basic compounds are for example amines, phosphines and ammonium,phosphonium or arsonium hydroxides. Inorganic basic compounds arepreferred. The expression “inorganic compounds” is understood to meancompounds which do not contain a carbon-hydrogen bond. The inorganicbasic compound may be chosen from alkali and alkaline-earth metaloxides, hydroxides, carbonates, hydrogencarbonates, phosphates,hydrogenphosphates and borates, and mixtures thereof. Alkali andalkaline-earth metal oxides and hydroxides are preferred. Differentbasic compounds may be used in the various reaction zones where thereaction of step a) is carried out.

Generally, the temperature, reaction time or residence time and themolar ratio of dichloropropanol to the basic compound are higher in thereaction zones where the 2,3-dichloro-1-propanol/1,3-dichloro-2-propanolratio is higher.

Step a) may be followed by an operation for neutralizing the excessbasic compound.

It is possible to combine step a) or part of step a) with step b) in acommon device compartmentalized into various reaction and settlingzones.

The first fraction separated in step b) may have a composition such asthat described for the first fraction separated in step b) of theepichlorohydrin manufacturing process which is the subject of PatentApplications FR 07/53375 and 075/55448 in the name of Solvay SA, ofwhich the content is incorporated here by reference.

The first fraction separated in step b) may contain, besidesepichlorohydrin and trichloropropane, other organic compounds such as,for example, halogenated hydrocarbons other than trichloropropane,chloroacetone and methyl glycidyl ether, glycerol, hydroxyacetone,glycidol, acetaldehyde, acrolein, acetone, ethylene oxide, propyleneoxide and 2-butanone. These compounds may come from the dichloropropanolmanufacturing process and/or be formed during the reaction betweendichloropropanol and the basic compound during step a) of the processaccording to the invention.

The first fraction separated in step b) generally contains at least 100g of epichlorohydrin/kg of first fraction, preferably at least 200 g/kg,even more preferably at least 300 g/kg, still more preferably at least400 g/kg, more particularly preferably at least 500 g/kg, even moreparticularly preferably at least 600 g/kg, still more particularlypreferably at least 700 g/kg, most particularly preferably at least 800g/kg and very most particularly preferably at least 850 g/kg. Theepichlorohydrin content of the first fraction separated is generally atmost 900 g/kg. The epichlorohydrin content of the first fractionseparated depends, for example, on the use of an organic solvent and/oron an incomplete conversion of the mixture of 1,3-dichloro-2-propanoland 2,3-dichloro-1-propanol.

The first fraction separated in step b) generally contains at most 2 gof chloroacetone/kg of first fraction and usually at most 0.3 g/kg,commonly at most 0.1 g/kg, and particularly preferably at most 0.05g/kg. The chloroacetone content is generally at least 0.005 g/kg.

The first fraction separated in step b) generally contains at most 5 gof acrolein/kg of first fraction, usually at most 0.3 g/kg and commonlyat most 0.1 g/kg. The acrolein content is generally at least 0.07 g/kg.

The first fraction separated in step b) generally contains at most 20 gof chloroethers/kg of first fraction, usually at most 5 g/kg, commonlyat most 2 g/kg, and particularly preferably at most 1 g/kg. The contentof chloroethers is generally at least 0.5 g/kg.

Chloroethers are compounds of which the molecule comprises at least onechlorine atom and at least one oxygen atom, this oxygen atom beingbonded to two carbon atoms. Epichlorohydrin is not considered here as achloroether. These chloroethers preferably contain six carbon atoms.These chloroethers preferably contain two, sometimes three, chlorineatoms. These chloroethers preferably contain two oxygen atoms. Thesechloroethers are preferably chosen from compounds of crude chemicalformula: C₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂, and mixtures ofat least two of them.

The first fraction separated in step b) contains generally at most 10 gof chloroether of crude formula C₆H₁₀Cl₂O₂/kg of first fraction, usuallyat most g/kg, commonly at most 0.5 g/kg, and particularly preferably atmost 0.1 g/kg. The content of this chloroether is generally at least0.05 g/kg.

The first fraction separated in step b) contains generally at most 5 gof chloroether of crude formula C₆H₁₂Cl₂O/kg of first fraction, usuallyat most 2 g/kg, commonly at most 0.5 g/kg, and particularly preferablyat most 0.1 g/kg. The content of this chloroether is generally at least0.05 g/kg.

The first fraction separated in step b) contains generally at most 5 gof chloroether of crude formula C₆H₉Cl₃O₂/kg of first fraction, usuallyat most 2 g/kg, commonly at most 0.5 g/kg, and particularly preferablyat most 0.1 g/kg. The content of this chloroether is generally at least0.02 g/kg.

The first fraction separated in step b) contains generally at most 5 gof chloroether of crude formula C₆H₁₁Cl₃O₂/kg of first fraction, usuallyat most 2 g/kg, commonly at most 1 g/kg, and particularly preferably atmost 0.6 g/kg. The content of this chloroether is generally at least 0.5g/kg.

The first fraction separated in step b) generally contains other organiccompounds such as, for example, 1,3-dichloro-2-propanol,2,3-dichloro-1-propanol and mixtures thereof. The sum of the contents ofthese dichloropropanols is generally less than or equal to 900 g/kg offirst fraction, usually less than or equal to 800 g/kg, commonly lessthan or equal to 700 g/kg, in many cases less than or equal to 500 g/kg,often less than or equal to 300 g/kg and frequently less than or equalto 200 g/kg. The sum of the contents of these dichloropropanols isgenerally at least 90 g/kg.

The first fraction separated in step b) generally contains other organiccompounds in addition to the epichlorohydrin, chloroacetone, acrolein,chloroethers and dichloropropanols.

The latter may come from the dichloropropanol manufacturing processand/or be formed during the reaction between dichloropropanol and thebasic compound during step a) of the process according to the invention.Examples of these compounds are glycerol, 3-chloro-1,2-propanediol,2-chloro-1,3-propanediol, and mixtures thereof, hydroxyacetone,glycidol, methyl glycidyl ether, 1,2,3-trichloropropane, cis- andtrans-1,3-dichloropropenes, 1,3-dichloropropane and2-chloro-2-propen-1-ol.

The sum of the contents of glycerol, hydroxyacetone and glycidol isgenerally at most 100 g/kg of first fraction, usually at most 50 g/kg,commonly at most 30 g/kg, in particular at most 10 g/kg and specificallyat most 1 g/kg. The sum of these contents is generally at least 0.1g/kg.

The sum of the contents of 3-chloro-1,2-propanediol and2-chloro-1,3-propanediol is generally at most 5 g/kg of first fraction,usually at most 3 g/kg, and commonly at most 1 g/kg. This sum isgenerally at least 0.5 g/kg.

The methyl glycidyl ether content is generally at most 5 g/kg of firstfraction, usually at most 3 g/kg, and commonly at most 1 g/kg. Thiscontent is generally at least 0.005 g/kg.

The 1,2,3-trichloropropane content is generally at most 10 g/kg of firstfraction, usually at most 5 g/kg, commonly at most 3 g/kg andparticularly preferably at most 1 g/kg. This content is generally atleast 0.0001 g/kg.

The sum of the contents of cis- and trans-1,3-dichloropropenes isgenerally at most 2 g/kg of first fraction, usually at most 1 g/kg, andcommonly at most 0.1 g/kg. This sum is generally at least 0.01 g/kg.

The 1,3-dichloropropane content is generally at most 2 g/kg of firstfraction, usually at most 1 g/kg, and commonly at most 0.5 g/kg. Thiscontent is generally at least 0.001 g/kg.

The 2-chloro-2-propen-1-ol content is generally at most 2 g/kg of firstfraction, usually at most 1 g/kg, and commonly at most 0.5 g/kg. Thiscontent is generally at least 0.01 g/kg.

The first fraction separated in step b) generally contains water andinorganic compounds such as the basic compound and the salt.

The water content is generally at most 90 g/kg of first fraction,usually at most 80 g/kg, commonly at most 50 g/kg, often at most 30 g/kgand frequently at most 15 g/kg. The water content is generally at least1 g/kg of first fraction.

The salt content is generally at most 10 g/kg of first fraction,commonly at most 5 g/kg, usually at most 2 g/kg, often at most 0.1 g/kgand frequently at most 0.015 g/kg. This salt content is generally atleast 0.01 g/kg.

The proportion of salt present in the part of the liquid reaction mediumfrom step a) before the settling step b) which is found in the firstfraction separated in step b) is generally at most 25%, preferably atmost 10% and more preferably at most 5%.

The salts are preferably chosen from alkali or alkaline-earth metalchlorides, sulphates, hydrogensulphates, hydroxides, carbonates,hydrogencarbonates, phosphates, hydrogenphosphates and borates, andmixtures thereof. Alkali and alkaline-earth metal chlorides arepreferred. Calcium chloride and sodium chloride are more preferred.Sodium chloride is the most preferred salt.

The first fraction separated in step b) may also contain an acidcompound. The acid compound may be chosen from monobasic and polybasic,organic and inorganic acids and mixtures thereof. Polybasic acids may befound in variously protonated forms. Inorganic acids are preferred. Theexpression “inorganic acid” is understood to mean acids of which themolecule does not contain a carbon-hydrogen bond, such as hydrogenchloride, carbonic acid and its acid salts, sulphuric acid and its acidsalts, phosphoric acid and its acid salts and boric acid and its acidsalts. Hydrogen chloride is preferred. This acid may be added to thepart of the reaction medium from step a) as described in Application FR07/53375 filed in the name Solvay SA.

The second fraction separated in step b) may have a composition such asthat described for the second fraction separated in step b) of theepichlorohydrin manufacturing process which is the subject of PatentApplications FR 07/53375 and 07/55448 in the name of Solvay SA, of whichthe content is incorporated here by reference.

Among the supplementary treatments from step c), the liquid/liquidextraction, adsorption and distillation operations, alone or incombination, are preferred and the liquid/liquid extraction anddistillation operations, alone or in combination, are particularlypreferred.

In a first embodiment of step c) of the process for manufacturing theproduct according to the invention, the treatment from step c) comprisesat least one liquid/liquid extraction operation for the first fractionseparated in step b).

The extraction operation may be carried out cocurrently orcountercurrently.

The cocurrent operation is generally carried out in at least one stirredreactor, followed by a settling tank. The countercurrent operation isgenerally carried out in at least one extraction column. Various type ofreactors, settling tanks and extraction columns may be used, such asthose described in “Perry's Chemical Engineers' Handbook”, SixthEdition, section 21, pp. 21, 55 and following”.

The extraction solvent may be an organic composition or an aqueouscomposition.

The extraction solvent is often an aqueous composition. Besides water,the aqueous composition may contain other compounds such as salts and/orbasic compounds and/or acid compounds such as defined above and/ordichloropropanol. Frequently, the aqueous composition is essentiallycomposed of water, particularly demineralised water.

After the extraction, a first part containing most of theepichlorohydrin which was contained in the first fraction before theextraction operation, and a second part containing most of theextraction solvent, are separated.

The proportion of epichlorohydrin present in the first fractionseparated at the end of the settling step b) of the process according tothe invention before the liquid/liquid extraction operation from stepc), and which is found in the first part separated in step c), ispreferably at least 80%, more preferably at least 90% and even morepreferably at least 95%. These proportions are more particularlyobtained when the extraction solvent is an aqueous composition.

The epichlorohydrin content of the first part separated in step c) isgenerally greater than 900 g of epichlorohydrin per kg of first part,preferably greater than or equal to 950 g/kg, more preferably greaterthan or equal to 990 g/kg and most particularly preferably greater thanor equal to 999 g/kg. These contents are more particularly obtained whenthe extraction solvent is an aqueous composition.

The water content of the first part is generally less than or equal to150 g of water per kg of first part, usually less than or equal to 100g/kg, commonly less than or equal to 10 g/kg and particularly less than1 g/kg.

These contents are more particularly obtained when the extractionsolvent is an aqueous composition.

The content of organic extraction solvent from the first part separatedin step c) is generally less than or equal to 100 g per kg of firstpart, usually less than or equal to 50 g/kg and particularly less thanor equal to 1 g/kg.

The first part obtained at the end of the liquid/liquid extractiontreatment from step c) may constitute the product according to theinvention, in particular when the extraction solvent is water. Thisfirst part preferably constitutes the product according to theinvention.

The first part separated in step c) may be subjected to subsequenttreatments such as, for example, distillation, evaporation or strippingoperations.

The second part separated in step c) generally contains the basiccompound used in step a) of the process and/or the acid compound addedbefore the settling step b) and/or the salt used and/or formed in stepa) of the process, in particular when the extraction solvent is anaqueous composition.

The proportion of basic compound present in the first fraction separatedat the end of the settling step b) of the process according to theinvention before the liquid/liquid extraction operation from step c),and which is found in the second part separated in step c), is generallyat least 80%, preferably at least 90% and more preferably at least 95%.

The proportion of salt present in the first fraction separated at theend of the settling step b) of the process according to the inventionbefore the liquid/liquid extraction operation from step c), and which isfound in the second part separated in step c), is generally at least80%, preferably at least 90% and more preferably at least 95%.

These proportions are more particularly obtained when the extractionsolvent is an aqueous composition.

The second part separated in step c) may be partially or completelyrecycled to step a), and/or after step a) and before step b) of theprocess. That second part is often recycled after step a) and beforestep b), frequently in the operation for neutralizing the excess basiccompound after step a).

The second part separated in step c) may be subjected to a stripping,evaporation or distillation operation that makes it possible to recoverthe epichlorohydrin dissolved in this part.

In a second embodiment of step c) of the process for manufacturing theproduct according to the invention, in step c) the first fractionseparated in step b) is subjected to a treatment which comprises atleast one distillation operation, preferably at least two distillationoperations and more preferably at least two distillation operations ofwhich at least one is an operation for drying by azeotropicdistillation. This treatment preferably comprises at least twodistillation operations and more preferably at least four distillationoperations and most particularly preferably at least six distillationoperations in addition to the azeotropic distillation drying operation.

The expression “distillation operation” is understood to mean theseparation of a mixture into two fractions of different compositions bya series of evaporation and condensation operations interconnectedcountercurrently and carried out in a specific device or in one part ofa specific device. In the case where the separation of a mixture into Nfractions of different compositions is carried out in a single physicaljacket, it is considered that this corresponds to N−1 distillations.

The operation for drying by azeotropic, preferably heteroazeotropic,distillation with removal of an aqueous phase and of an organic phase,preferably with removal of an aqueous phase, may be carried out beforethe other distillation operations. The azeotropic distillation dryingoperation may be carried out after one or more of the other distillationoperations.

In this second embodiment, after the treatment from step c), twoportions are obtained.

In this second embodiment, the proportion of epichlorohydrin present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the first portion separated in step c), isgenerally at least 80%, preferably at least 90% and more preferably atleast 95%.

In this second embodiment, the proportion of dichloropropanol present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the second portion separated in step c), isgenerally at least 80%, preferably at least 90% and more preferably atleast 95%.

In this second embodiment, the first portion obtained at the end of thedistillation operations of the treatment from step c) may constitute theproduct according to the invention. This first portion preferablyconstitutes the product according to the invention.

In this second embodiment, the second portion may be partially orcompletely recycled to step a) of the process to obtain the productaccording to the invention.

In a third embodiment of step c) of the process for manufacturing theproduct according to the invention, in step c) the first fractionseparated in step b) is subjected to a treatment which comprises atleast one adsorption operation and at least one distillation operation,and preferably at least three distillation operations and morepreferably at least five distillation operations.

The expression “distillation operation” is understood to mean theseparation of a mixture into two fractions having different compositionsby a series of evaporation and condensation operations interconnectedcountercurrently and carried out in a specific device or in one part ofa specific device. In the case where the separation of a mixture into Nfractions of different compositions is carried out in a single physicaljacket, it is considered that this corresponds to N−1 distillations.

In this third embodiment, the adsorption operation may be carried outbefore the distillation operations. The adsorption operation may becarried out after one or more distillation operations. The object of theadsorption operation is generally to reduce the water content of thefractions treated. The adsorbants generally used are adsorbants such asmolecular sieves 3A, 4A and 5A.

In this third embodiment, after the treatment from step c), two cuts areobtained.

In this third embodiment, the proportion of epichlorohydrin present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the first cut separated in step c), is generallyat least 80%, preferably at least 90% and more preferably at least 95%.

In this third embodiment, the proportion of dichloropropanol present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the second cut separated in step c), is generallyat least 80%, preferably at least 90% and more preferably at least 95%.

In this third embodiment, separated at the end of the treatmentsdescribed in the second and third embodiments is epichloroydrin, ofwhich the water content is generally less than 0.5 g of water per kg ofepichlorohydrin, usually less than or equal to 0.1 g/kg and commonlyless than or equal to 0.05 g/kg. In this epichlorohydrin, the content oforganic compounds having a boiling point under a pressure of 1 barabsolute less than or equal to the boiling point of epichlorohydrin isgenerally less than or equal to 0.3 g of these compounds per kg ofepichlorohydrin, usually less than or equal to 0.2 g/kg and commonlyless than or equal to 0.1 g/kg. These compounds are, for example,acrolein, methyl glycidyl ether and chlororacetone. In thisepichlorohydrin, the content of organic compounds having a boiling pointunder a pressure of 1 bar absolute greater than or equal to the boilingpoint of epichlorohydrin is generally less than or equal to 0.7 g ofthese compounds per kg of epichlorohydrin, usually less than or equal to0.5 g/kg and commonly less than or equal to 0.3 g/kg. These compoundsare, for example, 2-chloro-2-propen-1-ol, dichloropropene,dichloropropane, hydroxyacetone, trichloropropane, glycidol,dichloropropanol, monochloropropanediol, glycerol and chloroethers suchas mentioned above.

In this third embodiment, the first cut obtained at the end of thetreatment from step c) may constitute the product according to theinvention. This first portion preferably constitutes the productaccording to the invention

In a fourth embodiment of step c) of the process for manufacturing theproduct according to the invention, which is preferred, the first andsecond embodiments are combined and in one preferred variant, initially,the first fraction separated in step b) is subjected to at least oneliquid/liquid extraction operation with an aqueous composition and inwhich a first part containing most of the epichlorohydrin which wascontained in the first fraction before the extraction operation isseparated, and this first part is subjected to at least one treatmentwhich comprises at least one operation for drying by azeotropicdistillation and at least one distillation operation.

In this fourth embodiment, after the treatment from step c), two cutsare obtained.

In this fourth embodiment, the proportion of epichlorohydrin present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the first cut separated in step c), is generallyat least 80%, preferably at least 90% and more preferably at least 95%.

In this fourth embodiment, the proportion of dichloropropanol present inthe first fraction separated at the end of the settling step b) of theprocess according to the invention before the treatment from step c),and which is found in the second cut separated in step c), is generallyat least 80%, preferably at least 90% and more preferably at least 95%.

In this fourth embodiment, separated at the end of the treatment fromstep c) is epichloroydrin, of which the water content is generally lessthan 0.5 g of water per kg of epichlorohydrin, usually less than orequal to 0.1 g/kg and commonly less than or equal to 0.05 g/kg. In thisepichlorohydrin, the content of organic compounds having a boiling pointunder a pressure of 1 bar absolute less than or equal to the boilingpoint of epichlorohydrin is generally less than or equal to 0.3 g ofthese compounds per kg of epichlorohydrin, usually less than or equal to0.2 g/kg and commonly less than or equal to 0.1 g/kg. In thisepichlorohydrin, the content of organic compounds having a boiling pointunder a pressure of 1 bar absolute greater than or equal to the boilingpoint of epichlorohydrin is generally less than or equal to 0.7 g ofthese compounds per kg of epichlorohydrin, usually less than or equal to0.5 g/kg and commonly less than or equal to 0.3 g/kg.

In this fourth embodiment, the first cut obtained at the end of thetreatment from step c) may constitute the product according to theinvention. This first cut preferably constitutes the product accordingto the invention.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1: first scheme of an installation used for obtaining the productaccording to the invention

FIG. 2: second scheme of an installation used for obtaining the productaccording to the invention

FIG. 3: third scheme of an installation used for obtaining the productaccording to the invention

FIG. 4: examples of chemical formula of epoxy resins

FIG. 5: examples of chemical formula of compounds having at least onearomatic hydroxyl group

FIG. 6: examples of chemical formula of compounds having at least onearomatic hydroxyl or aromatic amine group per molecule

FIG. 7: examples of chemical formula of polycyclopentadiene polyphenolsor aromatic polyamines

FIG. 8: example of chemical formula of a coagulant molecule

FIG. 9: example of chemical formula of wet-strength resin polymers

FIG. 10: example of chemical formula of compounds used as phosphoruscontaining flame retardants.

FIG. 1 shows a first scheme of an installation used for obtaining theproduct according to the invention.

In a first variant of this first scheme, a first reactor (1) is suppliedwith a first stream of dichloropropanol via the line (2) and a firststream of basic compound via the line (3). Drawn off from the reactor(1) via the line (4) is a stream comprising epichlorohydrin, salt,dichloropropanol and basic compound which have not reacted, and a secondreactor (5) is supplied with this stream. The reactor (5) is suppliedwith a second stream of dichloropropanol via the line (6) and with asecond stream of basic compound via the line (7). Drawn off from thesecond reactor (5) via the line (8) is a stream comprisingepichlorohydrin and salt, and a first settling tank (9) is supplied withthis stream. In the first settling tank (9), a first fraction containingmost of the epichlorohydrin contained in the stream (8) and a secondfraction containing most of the salt which was contained in the stream(8) are separated. The second fraction is drawn off from the settlingtank (9) via the line (10) and the first fraction via the line (11). Afirst part of the first fraction drawn off from the line (11) supplies afirst extractor (13) via the line (12). The first extractor (13) is alsosupplied with water via the line (14). Vigorous stirring is carried outin the first extractor (13). A stream is drawn off from the extractor(13) via the line (15) and a second settling tank (16) is supplied withthis stream. Drawn off from the second settling tank (16) via the line(17) is a third fraction containing most of the epichlorohydrincontained in the stream (15) and a fourth fraction containing water andthe salts via the line (18).

In various aspects of this first variant of this first scheme, a portionof the fourth fraction containing water and the salts, drawn off via theline (18), is respectively recycled to the first reactor (1) via theline (19) and/or between the first reactor (1) and the second reactor(5) via the line (20) and/or between the second reactor (5) and thefirst settling tank (9) via the line (21).

In a second variant of this first scheme, the procedure from the firstvariant is followed except that the first fraction drawn off from thefirst settling tank (9) via the line (11) no longer supplies theextractor (13) but supplies an extraction column (23) via the line (22).The extraction column (23) is supplied countercurrently with water viathe line (24). Drawn off from the column (23) is a fifth fractioncontaining most of the epichlorohydrin contained in the stream (22), viathe line (25), and a sixth fraction containing water and the salts, viathe line (26).

In various aspects of this second variant of this first scheme, aportion of the second fraction containing water and the salts, drawn offvia the line (26), is respectively recycled to the first reactor (1) viathe line (27) and/or to the second reactor (5) via the line (28) and/orbetween the second reactor (5) and the first settling tank (9) via theline (29).

In third and fourth variants of this first scheme, the procedure fromthe first variant or from the second variant respectively is followed,and in addition, a third reactor (30) is supplied with a third stream ofdichloropropanol via the line (31) and a third stream of basic compoundvia the line (32). Drawn off from the reactor (30) via the line (33) isa stream comprising epichlorohydrin, salt, dichloropropanol and basiccompound which have not reacted, and a fourth reactor (34) is suppliedwith this stream. The fourth reactor (34) is supplied with a fourthstream of dichloropropanol via the line (35) and with a fourth stream ofbasic compound via the line (36). Drawn off from the fourth reactor (34)via the line (37) is a stream comprising epichlorohydrin and salt, andthe first settling tank (9) is supplied with this stream.

In various aspects of these third and fourth variants of thisembodiment, the third reactor (30) is supplied with steam via the line(38) and drawn off from the third reactor (30), via the line (39), is astream containing water and epichlorohydrin, and/or the fourth reactor(34) is supplied with steam via the line (40) and drawn off from thefourth reactor (34), via the line (41), is a stream containing water andepichlorohydrin.

In these various variants, part of the streams (18) and/or (26) maysupply a purge via the lines (42) and (43) respectively.

Without being bound by any theory, one believes that in the a mixture ofdichloropropanol containing 1,3-dichloro-2-propanol and2,3-dichloro-1-propanol, the 1,3-dichloro-2-propanol isomer is mainlyconverted into epichlorohydrin in the first reactors (1) and/or (30),while the 2,3-dichloro-1-propanol isomer is mainly converted intoepichlorohydrin in the second reactors (5) and/or (34).

FIG. 2 shows a second scheme of an installation used for obtaining theproduct according to the invention.

In a first variant of this second scheme, an azeotropic drying column(50) is supplied with a stream containing epichlorohydrin via the line(51). This stream comes from one or more lines of the installationdescribed in FIG. 1, i.e. the lines (17), (25) and also the organicfraction of the lines (39) and (41). This stream contains, besidesepichlorohydrin, light products, that is to say of which the boilingpoint under a pressure of 1 bar absolute is below the boiling point ofepichlorohydrin, such as acetaldehyde and acrolein, water, heavyproducts, that is to say of which the boiling point under a pressure of1 bar absolute is above the boiling point of epichlorohydrin and belowthe boiling point of dichloropropanol, such as glycidol,2-chloro-2-propen-1-ol, hydroxyacetone, chloroacetone,1,3-dichloropropane, 1,3-dichloropropene, 1,2,3-trichloropropane,2-methyl-2-cyclopenten-1-one, cyclopentanone, 2-chloroethanol andchloropropanol, and super-heavy products, that is to say of which theboiling point under a pressure of 1 bar absolute is above the boilingpoint of dichloropropanol, such as monochloropropanediol and partiallychlorinated and/or esterified glycerol oligomers.

Drawn off from the column (50) via the line (52) is a stream containingwater, epichlorohydrin, light products and heavy products that form anazeotrope with water, and a first condenser (53), then a first settlingtank (55), are supplied with this stream via the line (54). Drawn offfrom the first settling tank (55) is a water phase, via the line (56),and epichlorohydrin saturated with water, via the line (57). The waterphase can be further sent to a High Temperature Oxidation treatmentUnit. A first part of the stream drawn off via the line (57) optionallysupplies the distillation column (50) via the line (58). A second partof the stream drawn off via the line (57) supplies a second distillationcolumn (60) via the line (59). Drawn off from the second column (60) viathe line (61) is a stream which essentially contains light products anda second condenser (96), then a second settling tank (97), are suppliedwith this stream via the line (61). Drawn off from the second settlingtank (97) is a gas phase containing light products, via the line (99)which can be further sent to a High Temperature Oxidation treatmentUnit. Drawn off from the second settling tank (97) is a water phase, viathe line (98) which can be further sent to a High Temperature Oxidationtreatment Unit. A part of the liquid contained in the settling tank(97), preferably of the organic phase, can be returned to the top of thedistillation column (60) via the line (106). Drawn off from the seconddistillation column (60) via the line (62) is a stream containing mainlyepichlorohydrin, and the first distillation column (50) is supplied withthis stream.

Drawn off from the column (50) via the line (63) is a stream scrubbed ofwater, and a third distillation column (64) is supplied with thisstream.

Drawn off from the third column (64) via the line (65) is a streamcontaining epichlorohydrin, light products and heavy products. Thisstream supplies a fourth distillation column (66) drawn off from which,via the line (67), is a stream that essentially contains light products.One part of this stream may be returned to the first distillation column(50) via the line (68). Drawn off from the fourth distillation column(66) via the line (69) is a stream depleted of light compounds, and afifth distillation column (70) is supplied with this stream. Drawn offfrom the fifth distillation column (70) via the line (71) is purifiedepichlorohydrin and via the line (72) a stream comprising heavy productsof which one part may be conveyed to the third distillation column (64)via the line (73).

Drawn off from the third column (64) via the line (74) is a streamcomprising epichlorohydrin, heavy products, dichloropropanol andsuper-heavy products, and a sixth distillation column (75) is suppliedwith this stream. Drawn off from the sixth distillation column (75) viathe line (76) is a stream containing epichlorohydrin and heavy products,and a twelfth distillation column (100) is supplied with this stream anddrawn off from the sixth distillation column (75) via the line (77) is astream containing dichloropropanol and super-heavy products, and aseventh distillation column (78) is supplied with this stream.

Drawn off from the twelfth distillation column (100) via the line (102)is a stream containing epichlorohydrin and that stream is recycled backto the first distillation column (50). Drawn off from the twelfthdistillation column (100) via the line (101) is a stream containingheavy products and that stream can be further treated in a HighOxidation Temperature Unit.

Drawn off from the seventh distillation column (78) via the line (79) isa stream of dichloropropanol, and via the line (80) a stream containingsuper-heavy products. The stream of dichloropropanol collected via theline (79) may be conveyed to one or more of the reactors (1), (5), (30)and (34) of the installation described in FIG. 1. The stream containingsuper-heavy products can be sent for further treatment a HighTemperature Oxidation Unit.

In a second variant of the second scheme, the procedure from the firstvariant is followed except that the lines and columns (74) to (80) areabsent and drawn off from the third column (64) via the line (81) is astream comprising epichlorohydrin, heavy products, dichloropropanol andsuper-heavy products, and an eighth distillation column (82) is suppliedwith this stream. Drawn off from the eighth distillation column (82) viathe line (83) is a stream containing super-heavy products, which can befurther treated in a High Temperature Oxidation Unit and via the line(84) a stream containing epichlorohydrin, heavy products anddichloropropanol, and a ninth distillation column (85) is supplied withthis stream.

Drawn off from the ninth distillation column (85) via the line (86) is astream of dichloropropanol, and via the line (87) a stream containingepichlorohydrin and heavy products, and the twelfth distillation column100 is supplied with this stream. The stream of dichloropropanolcollected via the line (86) may be conveyed to one or more of thereactors (1), (5), (30) and (34) of the installation described in FIG.1.

In a third variant of this second scheme, the procedure from the firstvariant is followed except that the lines and columns (65) to (73) areabsent.

Drawn off from the third column (64) via the line (88) is a streamcontaining epichlorohydrin, light products and heavy products. Thisstream supplies a tenth distillation column (89) drawn off from which,via the line (90), is a stream that contains heavy products. One part ofthis stream may be returned to the third distillation column (64) viathe line (91). Drawn off from the tenth distillation column (89) via theline (92) is a stream containing epichlorohydrin and light products, andan eleventh distillation column (93) is supplied with this stream. Drawnoff from the eleventh distillation column (93) via the line (94) is astream of purified epichlorohydrin, and via the line (95) a streamcontaining light compounds. One part of this stream may be conveyed tothe first distillation column (50) via the line (96).

In a fourth variant of this second scheme, the procedure from the secondvariant is followed except that the lines and columns (65) to (73) areabsent.

Drawn off from the third column (64) via the line (88) is a streamcontaining epichlorohydrin, light products and heavy products. Thisstream supplies a tenth distillation column (89) drawn off from which,via the line (90), is a stream that contains heavy products. One part ofthis stream may be returned to the third distillation column (64) viathe line (91). Drawn off from the tenth distillation column (89) via theline (92) is a stream containing epichlorohydrin and light products, andan eleventh distillation column (93) is supplied with this stream. Drawnoff from the eleventh distillation column (93) via the line (94) is astream of purified epichlorohydrin, and via the line (95) a streamcontaining light compounds. One part of this stream may be conveyed tothe first distillation column (50) via the line (96).

In a fifth variant of this second scheme, the procedure from the firstvariant is followed except that the lines and columns (69) to (73) areabsent.

Drawn off from the third column (66) via the line (103) is a streamcontaining epichlorohydrin, via line (104) a stream containing heavyproducts a part of which can be recycled to the third distillationcolumn (64) via line (105).

FIG. 3 shows a third scheme of an installation used for obtaining theproduct according to the invention.

In a first variant of this third scheme, a first distillation column(200) is supplied with a stream containing epichlorohydrin via the line(201). This stream comes from one or more lines of the installationdescribed in FIG. 1, i.e. the lines (17) and (25), and the organicfraction of lines (39) and (41). This stream contains, besidesepichlorohydrin, light products, that is to say of which the boilingpoint under a pressure of 1 bar absolute is below the boiling point ofepichlorohydrin, such as acetaldehyde and acrolein, water, heavyproducts, that is to say of which the boiling point under a pressure of1 bar absolute is above the boiling point of epichlorohydrin and belowthe boiling point of dichloropropanol, such as glycidol,2-chloro-2-propen-1-ol, hydroxyacetone, chloroacetone,1,3-dichloropropane, 1,3-dichloropropene, 1,2,3-trichloropropane,2-methyl-2-cyclopenten-1-one, cyclopentanone, 2-chloroethanol andchloropropanol, dichloropropanol and super-heavy products, that is tosay of which the boiling point under a pressure of 1 bar absolute isabove the boiling point of dichloropropanol, such asmonochloropropanediol and partially chlorinated and/or esterifiedglycerol oligomers.

Drawn off from the distillation column (200) via the line (202) is astream containing epichlorohydrin, water, light compounds and heavycompounds, and an azeotropic drying column (203) is supplied with thisstream. Drawn off from the drying column (203) via the line (204) is astream containing epichlorohydrin and water that is conveyed to asettling tank (207) via a condenser (205) and via the line (206). Drawnoff from the settling tank (207) via the line (208) is a stream mostlycontaining water and, via the line (209) a stream mostly containingepichlorohydrin that is conveyed to the distillation column (200).

Drawn off from the azeotropic drying column (203) via the line (210) isa stream containing epichlorohydrin, light compounds and heavycompounds, and a second distillation column (211) is supplied with thisstream. Drawn off from the second distillation column (211) via the line(212) is a stream containing light compounds, and via the line (213) astream containing epichlorohydrin and heavy compounds, and a thirddistillation column (214) is supplied with this stream. Drawn off fromthe column (214) via the line (215) is a stream composed of purifiedepichlorohydrin, and via the line (216) a stream containing heavycompounds that are recycled to the first distillation column (200).

Drawn off from the first distillation column (200) via the line (217) isa stream containing dichloropropanol, heavy compounds and super-heavycompounds, and a fifth distillation column (218) is supplied with thisstream. Drawn off from the column (218) via the line (219) is a streamcontaining super-heavy products, and via the line (220) a streamcontaining dichloropropanol and heavy products, and a sixth distillationcolumn (221) is supplied with this stream. Drawn off from the column(221) via the line (222) is a stream mostly containing dichloropropanol,and via the line (223) a stream essentially containing heavy products.

The stream of dichloropropanol collected via the line (222) may beconveyed to one or more of the reactors (1), (5), (30) and (34) of theinstallation described in FIG. 1.

In a second variant of the third scheme, the procedure from the firstvariant is followed except that the lines and columns (217) to (223) areabsent and drawn off from the first column (200) via the line (224) is astream comprising heavy products, dichloropropanol and super-heavyproducts, and a seventh distillation column (225) is supplied with thisstream. Drawn off from the seventh distillation column (225) via theline (226) is a stream containing heavy products, and via the line (227)a stream containing super-heavy products and dichloropropanol, and aneighth distillation column (228) is supplied with this stream.

Drawn off from the eighth distillation column (228) via the line (229)is a stream of dichloropropanol, and via the line (230) a streamcontaining super-heavy products. The stream of dichloropropanolcollected via the line (229) may be conveyed to one or more of thereactors (1), (5), (30) and (34) of the installation described in FIG.1.

In a third variant of the third scheme, the procedure from the firstvariant is followed except that the lines and columns (210) to (216) areabsent.

Drawn off from the drying column (203) via the line (231) is a streamcontaining epichlorohydrin, light products and heavy products. Thisstream supplies a ninth distillation column (232) drawn off from which,via the line (233), is a stream that contains heavy products. Drawn offfrom the ninth distillation column (232) via the line (234) is a streamcontaining epichlorohydrin and light products, and a tenth distillationcolumn (235) is supplied with this stream. Drawn off from the tenthdistillation column (235) via the line (236) is a stream of purifiedepichlorohydrin, and via the line (237) a stream containing lightcompounds.

In a fourth variant of the third scheme, the procedure from the secondvariant is followed except that the lines and columns (210) to (216) areabsent.

Drawn off from the drying column (203) via the line (231) is a streamcontaining epichlorohydrin, light products and heavy products. Thisstream supplies an eighth distillation column (232) drawn off fromwhich, via the line (233), is a stream that contains heavy products.Drawn off from the eighth distillation column (232) via the line (234)is a stream containing epichlorohydrin and light products, and a ninthdistillation column (235) is supplied with this stream. Drawn off fromthe ninth distillation column (235) via the line (236) is a stream ofpurified epichlorohydrin, and via the line (237) a stream containinglight compounds.

Other variants of the various embodiments can easily be envisaged.

The invention also relates to the use of the epichlorohydrin-basedproduct described above as a reactant in a process for manufacturingepoxy resins, synthetic glycerol, polyamide-epichlorohydrin resins,chemical formulations for water treatment, such as polyacrylamides,polyamines and quaternary ammonium salts, epichlorohydrin elastomers,such as epichlorohydrin homopolymers, epichlorohydrin/ethylene oxidecopolymers and epichlorohydrin/ethylene oxide/allyl glycidyl etherterpolymers, glycidyl ethers, such as cresyl glycidyl, butyl, decyl ordodecyl ethers, surfactants, flame retardants, such as phosphorylatedflame retardants, resins for the production of water-resistant paper andglycidyl acrylates and methacrylates.

The presence of impurities in epichlorohydrin may prove troublesome insome of these applications for various reasons. Some halogenatedhydrocarbons for instance are or are suspected to be carcinogenic, aresuspected to have development toxicity, reproductive toxicity,cardiologic toxicity, endocrine toxicity, immunotoxicity and toxicity tothe liver, the kidneys, the nerves, the respiratory tract and to theskin. They can remain in the final products and possibly degrade with aconcomitant deterioration of the properties of the final products. Theycan exhibit or degrade in compounds exhibiting some toxicity leading tosafety issues especially when the final products are intended to be incontact with food and drink. Moreover, they can accumulate in andcontaminate industrial waters such as wastewaters for instance or watercontaining pulp that is recycled in the pulp and paper industry. In thelatter case, their higher concentration can increase contamination ofthe paper made using the recycled water.

A further goal of the invention is to solve those problems by providinga product containing epichlorohydrin and a reduced level of impuritieswhich can be used in the manufacture of epoxy derivatives, of productswhich will be used in food and drink applications, of cationizationagents, of flame retardants, of products which will be used as detergentingredients, and of epichlorohydrin elastomers.

The invention is therefore also related to the use of the productaccording to the invention in the manufacture of epoxy resins orglycidyl esters or glycidyl ethers or glycidyl amides or glycidyl imidesor coagulants or wet-strength resins or cationization agents or flameretardants or detergent ingredients or epichlorohydrin elastomers.

1. Epoxy Derivatives 1.1. General

Epoxy derivatives are for example, epoxy resins, glycidyl ethers,glycidyl esters and glycidyl amides and imides. Examples of glycidylesters are glycidyl acrylate and glycidyl methacrylate.

By epoxy resin, one intend to denote a polymer, the chemical formula ofwhich contains at least one oxirane group, preferably one2,3-epoxypropyloxy group.

By polymer, one intends to denote molecules with many units joined toeach other through chemical covalent bonds, often in a repeating manner,those units being referred as repeat units. The number of repeat unitsis higher than zero. A polymer contains at least one type of repeatunits. When the polymer contains only one type of repeat units, it iscalled a homopolymer. When the polymer contains more than one type ofrepeat units, it is called a copolymer. The copolymers can be of therandom type, of the alternating type or of the block type, such asdescribed in “Polymer Science Dictionary, M.S.M., Elsevier AppliedScience, London and New York 1989, page 86”.

Examples of chemical formulas of epoxy resins are presented in FIG. 4,where n is not zero.

By glycidyl ether, one intends to denote an ether, the chemical formulaof which contains at least one glycidyl (2,3-epoxypropyl) group andwhich is not a polymer. Examples of glycidyl ethers are N-butyl glycidylether, C₁₂-C₁₄ aliphatic glycidyl ethers, o-Cresol glycidyl ether,neopentylglycol diglycidyl ether and butanediol diglycidyl ether.

By glycidyl ester, one intends to denote an ester, the chemical formulaof which contains at least one glycidyl (2,3-epoxypropyl) group andwhich is not a polymer. Examples of glycidyl ester are diglycidyl esterof hexahydrophthalic acid, glycidyl ester of neodecanoic acid, glycidylacrylate and glycidyl methacrylate.

By glycidyl amides and imides, one intends to denote an amide or animide, the chemical formula of which contains at least one glycidyl(2,3-epoxypropyl) group and which is not a polymer. Examples of glycidylamide and imide1,3,5-tris(2,3-epoxypropyl)-1,3,5-perhydrotriazine-2,4,6-trione and5,5-dimethyl-1,3-bis(2,3-epoxypropyl)-2,4-imidazolidinedione.

1.2. Co-Reactants

When, the product containing epichlorohydrin according to the inventionis used in the manufacture of epoxy derivatives, the product containingepichlorohydrin is usually subjected to a reaction with at least onecompound containing at least one active hydrogen atom, preferably atleast two active hydrogen atoms, followed by dehydrochlorination asdescribed in Ullmann's Encyclopedia of Industrial Chemistry, 5thEdition, 1987, Vol. A9, pp. 547-553).

The compound containing one active hydrogen atom can be selected frommono alcohol, preferably from 1-butanol, a C₁₂ to C₁₄ primary alcohol ora cresol, and mixtures thereof, mono carboxylic acids, like for instanceneodecanoic acid, acrylic acid, methacrylic acid, or mixtures thereof.

The compound containing at least two active hydrogen atoms can beselected from polyols, polyamines, amino alcohols, polyimides andamides, polycarboxylic acids, and mixtures thereof.

The polyols can be aromatic or aliphatic. Aromatic polyols arepreferred.

Preferred aliphatic polyols are aliphatic diols, more preferablyselected from butanediol, neopentyl glycol, hydrogenated Bisphenol A(4,4′-dihydroxy-2,2-dicyclohexylpropane), and aliphatic triols,preferably glycerol, poly(oxypropylene) glycol, and mixtures thereof.

Aromatic polyols can be selected from polyhydroxy benzenes, polyphenoliccompounds, and mixtures thereof.

Poly hydroxybenzenes are preferably selected from dihydroxy benzenes,trihydroxy benzene, and mixtures thereof. Dihydroxy benzenes are morepreferably selected from 1,2-, 1,3-, 1,4-dihydroxy benzenes and mixturethereof.

Trihydroxy benzene is preferably 1,3,5-trihydroxy benzene.

Polyphenolic compounds are generally compounds the molecule of whichcontains at least one aromatic hydroxyl group.

Suitable compounds having at least one aromatic hydroxyl group which canbe employed herein are such as described in U.S. Pat. No. 4,499,255, thecontent of which is incorporated herein by reference and include, forexample, phenols, bisphenols, novolac resins, polyvinyl phenols, thecorresponding amine compounds and the like, such as those represented bythe formulas I to V of FIG. 5 wherein, each A is independently adivalent hydrocarbon group having from 1 to about 12, preferably from 1to about 6 carbon atoms, —O—, —S—, —S—S—,

—(S═O)₂—, —(S═O)— or —(C═O)—, A′ is a trivalent hydrocarbon group havingfrom 1 to about 12, preferably from 1 to about 6, carbon atoms; each Ris independently hydrogen, a hydrocarbyl group having from 1 to about10, preferably from 1 to about 4, carbon atoms, a halogen atom,preferably chlorine or bromine or a hydroxyl group or an amino group;each Z is independently —OH or NH2; p has a value of from about 1 toabout 100, preferably from about 2 to about 50; m has a value from about1.00 to about 6 and n has a value of zero or 1.

Also suitable as compounds having at least one aromatic hydroxyl oraromatic amine group per molecule are those represented by the formulasVI to VIII of FIG. 6, wherein each R is a divalent hydrocarbyl grouphaving from 1 to about 18, preferably from about 2 to about 12 and mostpreferably from about 2 to about 6 carbon atoms, a group represented bythe formulas IX, X, XI or XII of FIG. 6, or R can combine with R¹ so asto form a stable heterocyclic ring with the nitrogen atoms; each A isindependently a divalent hydrocarbyl group having from 1 to about 10,preferably from 1 to about four carbon atoms, —O—, —S—, —S—S—, —(S═O)₂—,—(S═O)— or —(C═O)—, each R¹ is independently hydrogen, a2,3,-epoxypropyl group, a 2-alkyl-2,3-epoxypropyl group, a monovalenthydrocarbyl group or a hydroxyl substituted monovalent hydrocarbylgroup, said hydrocarbyl groups having from 1 to about 9 carbon atoms,said alkyl having from 1 to about 4, preferably 1 to about 3 carbonatoms; each R² is independently hydrogen or an alkyl group having from 1to about 4, preferably 1 to about 3 carbon atoms; each R³ isindependently hydrogen or an alkyl group having from 1 to about 4 carbonatoms; each R⁴ is independently hydrogen, a hydrocarbyl or halogensubstituted hydrocarbyl group having from 1 to about 9, preferably from1 to about 2 carbon atoms; each R⁸ is independently selected from thegroup represented by formula XIV or the same groups as R¹ except that R⁸cannot be a hydrogen; each R⁹ is independently a divalent hydrocarbylgroup having from 2 to about 4, preferably 2 carbon atoms; each Z isindependently —OH or —NH2; each X is independently hydrogen, chlorine,bromine or a hydrocarbyl or a hydrocarbyloxy group having from 1 toabout 9, preferably 1 to about 6 carbon atoms; each m independently hasa value of zero or 1; n has an average value of from about 0.01 to about6, preferably 0.1 to about 4; p has an average value of from 1 to about10, preferably from 1 to about 3; q has an average value of at least 1,preferably from 1 to about 150, most preferably from 1 to about 100 andusually from 1 to about 10 and each y and z independently has a value of1 or 2.

Also suitable are polycyclopentadiene polyphenols or aromatic polyaminesrepresented by the formula XIII of FIG. 7, wherein Z is —OH or —NH2 andn has a value from 1 to about 5; n′ has a value of from about 1 to about10, preferably from 3 to about 6; each R is independently hydrogen, ahydrocarbyl group having from 1 to about 10, preferably from 1 to about4 carbon atoms, a halogen atom, preferably chlorine or bromine or ahydroxyl group or an amino group.

Suitable such polycyclopentadiene polyphenols and methods for theirpreparation can be found in U.S. Pat. No. 4,390,680 issued to Donald L.Nelson on Jun. 28, 1983 which is incorporated herein by reference. Thepolycyclo-pentadiene aromatic polyamines can be prepared in a similarmanner by substituting an aromatic amine for the phenolic compound.

Also suitable are compounds containing both at least one aromatichydroxyl group and at least one aromatic amine group such as, forexample, hydroxy aniline, aminoxylenol and the like.

The polyphenolic compound is preferably selected from Bisphenol A(4,4′-dihydroxy-2,2-diphenylpropane, 4,4′-isopropylidenediphenol),tetrabromo Bisphenol A (4,4′-isopropylidenebis(2,6-dibromophenol)),Bisphenol AF(4,4′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bisphenol)=hexafluorobisphenolA (4,4′-dihydroxy-2,2-diphenyl-1,1,1,3,3,3-hexafluoropropane),1,1,2,2-tetra(p-hydroxyphenyl)ethane, hexafluorobisphenol A,tetramethylbisphenol (4,4′-dihydroxy-3,3′,5,5′-tetramethyl bisphenol),1,5-dihydroxynaphthalene, 1,1′,7,7′-tetrahydroxy-dinaphthyl methane,4,4′-dihydroxy-α-methylstilbene, a condensation product of Bisphenol Awith formaldehyde (Bisphenol A novolac), a condensation product ofphenol with formaldehyde, preferably Bisphenol F (mixture of o, o′, o,p′ and p, p′ isomers of dihydroxy diphenylmethane), a condensationproduct of cresol with formaldehyde (mixtures of o, o′, o, p′ and p, p′isomers of methyl hydroxy diphenylmethane), an alkylation product ofphenol and dicyclopentadiene (2,5-bis[(hydroxyphenyl]octahydro-4,7-methano-5H-indene), a condensation product ofphenol and glyoxal (tetrakis(4-hydroxy-phenyl)ethane), a condensationproduct of phenol and a hydroxybenzaldehyde (e.g.,tris(4-hydroxyphenyl)methane), 1,1,3-tris-(p-hydroxyphenyl)-propane, andmixtures thereof.

The polyamines can be aliphatic or aromatic. Aromatic diamines arepreferred, like for instance 4,4′-diamino diphenyl methane.

The amino alcohol can be aliphatic or aromatic. Aromatic amino alcoholare preferred like for instance, p-aminophenol.

The imides and amides can be aliphatic or aromatic. Heterocyclic imidesand amides are preferred, like for instance 1,3,5-triazinetriol andimidazolidine-2,4-dione.

Polycarboxylic acids can be aliphatic or aromatic. An example of dimericfatty acid is linoleic dimer acid. The polycarboxylic acid is preferablyan aromatic dicarboxylic acid like for instance hexahydrophthalic acid.

1.3. Processes for Making Epoxy Derivatives

The process for making epoxy resins, glycidyl ethers and glycidyl estersgenerally involve a reaction of the product containing epichlorohydrinand the compound containing at least one active hydrogen atom, followedby dehydrochlorination with a basic agent

The process for making epoxy resin usually involves two steps: thepreparation of an uncured epoxy resin followed by a curing step.

1.3.1. Uncured ER

The reaction between the product containing epichlorohydrin and thecompound containing at least one, preferably two active hydrogen atomscan be carried out by any process known in the art like for instance theCaustic Coupling Process and the phase-transfer catalyst process, formaking Liquid Epoxy Resins (LER), the Taffy and the Advancement orFusion process for making Solid Epoxy Resins (SER).

Caustic Coupling Process

In the caustic process, caustic is used as a catalyst for thenucleophilic ring-opening (coupling reaction) of the epoxide group onthe primary carbon atom of epichlorohydrin by the phenolic hydroxylgroup and as a dehydrochlorinating agent for conversion of thechlorohydrin to the epoxide group. Caustic (NaOH) can however besubstituted by any basic compound.

The epichlorohydrin and the compound with active hydrogen atom,preferably an aromatic hydroxyl or aromatic amine compound, are employedin a molar ratio of from about 2:1 to about 10:1, preferably from about2:1 to about 6:1, respectively.

The basic compound may be an organic or inorganic basic compound.Organic basic compounds are for example amines, phosphines and ammonium,phosphonium or arsonium hydroxides. Inorganic basic compounds arepreferred. The expression “inorganic compounds” is understood to meancompounds which do not contain a carbon-hydrogen bond. The inorganicbasic compound may be chosen from alkali and alkaline-earth metaloxides, hydroxides, carbonates, hydrogencarbonates, phosphates,hydrogenphosphates and borates, and mixtures thereof. Alkali andalkaline-earth metal oxides and hydroxides are preferred. Preferredalkali metal hydroxides which can be employed herein include, forexample, sodium hydroxide, potassium hydroxide, lithium hydroxide ormixtures thereof. Sodium hydroxide is especially preferred.

In the process according to the invention, the basic compound may be inthe form of a liquid, an essentially anhydrous solid, a hydrated solid,an aqueous and/or organic solution or an aqueous and/or organicsuspension. The basic compound is preferably in the form of anessentially anhydrous solid, a hydrated solid, an aqueous solution or anaqueous suspension. It is preferred to use a solution or a suspension,preferably a solution of the basic compound, preferably sodiumhydroxide, in water.

The content of the basic agent in the solution or suspension isgenerally higher than or equal to 5% by weight, preferably higher thanor equal to 10% by weight, preferably higher than or equal to 20% byweight, and most preferably higher than or equal to 30% by weight. Thatcontent is usually lower than or equal to 70% by weight, preferablylower than or equal to 60% by weight, preferably lower than or equal to50% by weight, and most preferably lower than or equal to 40% by weight.

The alkali metal hydroxide is preferably employed as an aqueoussolution, usually at a concentration of from about 20 to about 50,preferably from about 40 to about 50 percent by weight.

The amount of basic compound, preferably alkali metal hydroxide, whichis employed in the process of the present invention is from about 0.80mole to about 1.2 mole of basic agent, preferably from about 0.90 moleto 1.0 mole per each, preferably aromatic, hydroxyl group and,preferably aromatic, amine hydrogen.

The basic agent, epichlorohydrin and the compound containing activehydrogen atom can be mixed in any order. It is preferred to add thebasic compound to a mixture of the two other reactants. The basic agent,preferably, alkali metal hydroxide can be added either continuously orincrementally, but never is all of the alkali metal hydroxide added inone increment.

The reaction can be carried out in a solvent. Suitable solvents whichcan be employed include any solvent which does not react with anycomponent in the reaction mixture. Preferably such solvent is partiallyor wholly miscible with water, forms a codistillate with theepichlorohydrin and water and the distillate has a boiling point belowthat of the lowest boiling component of the reaction mixture at thepressure employed. Suitable such solvents include primary and secondaryalcohols such as, for example, 1-methoxy-2-hydroxy propane,1-butoxy-2-hydroxy ethane, cyclohexanol. The secondary alcohols arepreferred.

When a solvent is used, the amount of solvent which is employed willdepend on the particular solvent and the compound containing activehydrogen atom being employed. The solvent generally ranges from about 5to about 50 weight percent, preferably from about 10 to about 40 weightpercent based on the total weight of reactants.

The pressure can be equal to 1 bar absolute, lower than 1 bar absoluteor higher than 1 bar absolute. When a solvent is used, suitablepressures which can be employed are those which will provide thecodistillate with a boiling point of from about 45° C. to about 80° C.,preferably from about 55° C. to about 70° C.

The temperature of the reaction is usually greater than or equal to 25°C., preferably greater than or equal to 50° C., more preferably greaterthan or equal to 90° C., and most preferably greater than or equal to95° C. The temperature of the reaction is usually lower than or equal to200° C., preferably lower than or equal to 150° C., more preferablylower than or equal to 125° C., and most preferably lower than or equalto 120° C.

The reaction is usually conducted for a length of time such that thequantity of groups containing active hydrogen atom remaining in thereaction mixture is not greater than about 0.5, preferably not greaterthan about 0.2 percent by weight. That time is usually greater than orequal to 0.5 h, frequently greater than or equal to 1.0 h, often greaterthan or equal to 2.0 h, and most particularly greater than or equal to3.0 h. The time of reaction is usually lower than or equal to 20 h,often lower than or equal to 10 h, frequently lower than or equal to 5h, and most particularly lower than or equal to 4 h.

Upon completion of the reaction, the resultant epoxy resin is finishedin any of the methods normally employed. The excess epichlorohydrin isusually removed by distillation and the salt removed by filtration,centrifugation and/or water washing.

The epichlorohydrin distillation is generally carried out in two steps.The first step is carried out generally at atmospheric pressure (1 barabsolute), at a temperature usually greater than or equal to 100° C.,preferably greater than or equal to 120° C., more preferably greaterthan or equal to 130° C., and most preferably greater than or equal to145° C. and usually lower than or equal to 200° C., preferably lowerthan or equal to 180° C., more preferably lower than or equal to 175°C., and most preferably lower than or equal to 155° C. The second stepis carried out usually at a subatmospheric pressure, usually lower thanor equal to 0.1 bar absolute, preferably lower than or equal to 0.01bar, more preferably lower than or equal to 0.005 bar, and mostpreferably lower than or equal to 0.002 bar, at a temperature usuallygreater than or equal to 150° C., preferably greater than or equal to170° C., more preferably greater than or equal to 190° C., and mostpreferably greater than or equal to 195° C. and usually lower than orequal to 300° C., preferably lower than or equal to 250° C., morepreferably lower than or equal to 220° C., and most preferably lowerthan or equal to 215° C.

The salt which is formed can be separated from the crude product throughaddition of a solvent, e.g. toluene, followed by filtration anddistillation to remove the solvent.

Phase-Transfer Catalytic Process

Alternatively, in the Phase-Transfer Catalyst Process, the couplingreaction and dehydrochlorination can be performed separately by usingphase-transfer coupling catalysts, such as quaternary ammonium salts,which are not strong enough bases to promote dehydrochlorination. Oncethe coupling reaction is completed, caustic is added to carry out thedehydrochlorination step. Via this method, higher yields of for examplethe monomeric diglycidyl ether of Bisphenol A (DGEBA) (>90%) are readilyavailable.

Batch methods and preferably continuous or semi continuous processes canbe used.

Taffy Process

The Taffy method is used to prepare higher molecular weight solidresins. It is directly from epichlorohydrin, the compound containingactive hydrogen atoms, and a stoichiometric amount of NaOH. This processis very similar to the caustic coupling process used to prepare liquidepoxy resins. Lower epichlorohydrin to compound containing activehydrogen atoms ratios are used to promote formation of high molecularweight resins. Upon completion of the polymerization, the mixtureconsists of an alkaline brine solution and a water-resin emulsion. Theproduct is recovered by separating the phases, washing the resin withwater, and removing the water under vacuum.

The epichlorohydrin and the compound with active hydrogen atom,preferably an aromatic hydroxyl or aromatic amine compound, are employedin a molar ratio of from about 1:1 to about 2:1, preferably from about1.3:1 to about 1.8:1, respectively.

The alkali metal hydroxide is preferably employed as an aqueoussolution, usually at a concentration of from about 1 to about 20,preferably from about 5 to about 15 percent by weight.

The amount of basic compound, preferably alkali metal hydroxide, whichis employed in the process of the present invention is from about 0.05mole to about 2 mole of basic agent, preferably from about 0.1 mole to0.5 mole per each, preferably aromatic, hydroxyl group and, preferablyaromatic, amine hydrogen.

The temperature of the reaction is usually greater than or equal to 25°C., preferably greater than or equal to 50° C., more preferably greaterthan or equal to 90° C., and most preferably greater than or equal to95° C. The temperature of the reaction is usually lower than or equal to200° C., preferably lower than or equal to 150° C., more preferablylower than or equal to 125° C., and most preferably lower than or equalto 120° C.

The time of reaction is usually greater than or equal to 0.1 h,frequently greater than or equal to 0.5 h, often greater than or equalto 1.0 h, and most particularly greater than or equal to 1.5 h. The timeof reaction is usually lower than or equal to 20 h, often lower than orequal to 10 h, frequently lower than or equal to 5 h, and mostparticularly lower than or equal to 4 h.

The basic agent, epichlorohydrin and the compound containing activehydrogen atom can be mixed in any order. It is preferred to addepichlorohydrin to a mixture of the two other reactants.

The reaction is usually carried out under vigorous agitation.

At the end of the reaction, the mixture separates into two layers. Theheavier aqueous layer is drawn off and the molten, taffy-like product iswashed with hot water until the wash water is neutral. The taffy-likeproduct is dried at a temperature generally higher than or equal to 100°C., preferably higher than or equal to 120° C.

Alternatively, epichlorohydrin and water can be removed by distillationat temperatures up to 180° C. under vacuum. The crude resin/salt mixturecan then be dissolved in a secondary solvent to facilitate water washingand salt removal. The secondary solvent can then be removed via vacuumdistillation to obtain the product.

The advancement or fusion process is an alternative method for makingsolid epoxy resin and is based on the chain-extension reaction of liquidepoxy resin (for example, crude DGEBA) with bisphenol A.

1.3.2. Curing Agents

The curing of Epoxy Resins can be carried out using classical curingagents. The cure can be done with coreactive curing agents, or it can becatalytic or photoinitiated cationic.

The coreactive curing agents can be selected from amine functionalcuring agents, carboxylic functional polyester and anhydride curingagents, phenolic-terminated curing agents, melamine-, urea-, andphenol-formaldehyde resins, mercaptans (polysulfides and polymercaptans)curing agents, cyclic amidines curing agents, isocyanate curing agentsand cyanate ester curing agents

The amine functional curing agents can be primary and secondary amines,polyamides, amidoamines and dicyandiamide.

The amines can be aliphatic, cycloaliphatic, aromatic amines or arylylamines.

The aliphatic amines can be selected from liquid aliphatic polyamines,such as polyethylene polyamines, hexamethylene diamine, polyether amines(polyglycol-based polyamines), ketimines (reaction products of ketonesand primary aliphatic amines), mannich base adducts (reaction productsof amine, phenol and formaldehyde), polyetheramines (reaction product ofpolyols derived from ethylene or propylene oxide with amines) andmixtures thereof.

The cycloaliphatic amines can be selected from isophorone diamine,bis(4-amino-cyclohexyl)methane, 1,2-diamino-cyclohexane,trihexylmethylene diamines, metaxylylenediamine, and mixtures thereof.

The aromatic amines can be selected from meta-phenylenediamine,methylene dianiline, alkyl (tetraethyl-)-substituted methylenedianiline, 4,4′-diaminodiphenylmethane, 4,4′-diamino diphenyl sulfone,diethylenetoluenediamine

The arylyl amines can be selected from meta xylylenediamine,1,3-bis(aminomethyl cyclohexane).

The amine can be more specifically selected from diethylenetriamine,triethylenetetramine, Poly(oxypropylene diamine), poly(oxypropylenetriamine), poly(glycol amine), N-aminoethylpiperazine, isophoronediamine, 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane,4,4-diamino-diphenylmethane, 4,4-diaminodiphenyl sulfone,m-phenylenediamine, diethyltoluenediamine, meta-xylene diamine,1,3-bis(aminomethyl cyclohexane, and mixtures thereof.

The polyamides can be obtained by reaction of dimerized and trimerizedvegetable oil fatty acids (9,12 and 9,11-linoleic acids) with polyamines(diethylene triamine) or from polyamines and phenolic-containingcarboxylic acids (phenalkamines).

The amidoamines can be obtained by reaction of mono functional acid liketall-oil fatty acid with a polyamine such diethylenediamine.

The carboxylic functional polyester can be obtained by reaction ofterphthalic acid, trimellitic anhydride and neopentyl alcohol

The acid anhydrides can be phthalic anhydride, tetrahydrophthalicanhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalicanhydride, hexahydrophthalic anhydride, nadic methyl anhydride or methylhimic anhydride, benzophenonetetracarboxylic dianhydride,tetrachlorophthalic anhydride, and mixtures thereof.

The phenolic-terminated curing agents are products that can be obtainedby reaction of phenol, creseol or bisphenol a with formaldehydes.

The mercaptans (polysulfides and polymercaptans) curing agents generallycontain terminal thiols.

The cyclic amidines curing agents can be for instance 2-phenylimidazolidine.

The cyanate ester curing agents can be for instance bisphenol a dicyanteester.

The catalytic cure can be carried out with Lewis bases or Lewis acids.

The Lewis bases are for instance tertiary amine, like2-diethylamino-methylphenol, 2,4,6-tris(dimethylaminomethyl)phenol andimidazoles such as 2-methylimidazole and 2-phenylimidazole, cyclicamidines like 2-phenylimidazoline, substituted ureas like3-phenyl-1,1-dimethylurea and quaternary ammonium salt like tetralkyl-and alkyl-triphenyl phosphonium salts.

The Lewis acid can be selected from boron trilhalides, preferably borontrifluoride.

The Photoinitiated Cationic Cure can be carried out with photoinitiatorslike aryldiazonium salts, diaryldiazonium salts, diaryldiionium saltsand onium salts of Group VIa elements, such as triarylsulfonium salt,dialkylphenacyl sulfonium salts.

1.4 Uses of Epoxy Resins

The epoxy resins can be used in coating applications and in structuralapplications. The coating applications can be in the fields of marineand industrial maintenance (corrosion-resistant coatings for ships,shipping containers, offshore oil rigs and platforms, transportationinfrastructures such as bridges, rail car coatings, coatings forindustrial storage tanks, and primers for light industrial andagricultural equipment), metal container (aluminum and steel food andbeverage cans) and coil coatings (metal can ends, can bodies, buildingproducts, appliance panels, transportation, and metal furnitureapplications), automotive coatings (primer surface coatings) and inksand resists. Coating can be done using various technologies like lowsolids solventborne coating, high solid solventborne coating,solvent-free coating, waterborne coating, powder coating andradiation-curable coating.

The structural applications can be in the field of structural composites(fiber reinforcing materials based on glass, boron, graphite andaromatic polyaramides), of civil engineering, flooring (floor paints,self-leveling floors, trowelable floors, and pebble-finished floors) andconstruction, of electrical laminates, of electrical laminates (printedwiring boards and printed circuit boards), of other electrical andelectronic applications, like casting, potting, encapsulation(switchgear components, transformers, insulators, high voltage cableaccessories, and similar devices) and transfer molding (encapsulation ofelectronic components such as semiconductor chips, passive devices, andintegrated circuits), of adhesives (cohesion between similar anddissimilar materials such as metals, glass, ceramics, wood, cloth, andmany types of plastics) and of tooling (prototypes, master models, moldsand other parts for aerospace, automotive, foundry, boat building, andvarious industrial molded items).

1.5 Uses of Glycidyl Ethers and Esters

These products are used for applications such as coatings, adhesives andreactive diluents.

1.6 Uses of Glycidyl Amides and Imides

These products are used for applications such as outdoor powder coatingswith polyesters, or in applications in which a non-yellowing epoxy resinis desirable.

2. Products for Food-Drink Applications—Coagulants 2.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of products that will be used in applicationswhere they will come in contact with food and drink, more specificallyfor the manufacture of synthetic organic coagulants.

Coagulation refers to the reduction or elimination of electrostaticrepulsion forces between particles via addition of certain coagulants,and in technical terms, the first phase of floc formation after chemicalmixing and destabilization, but before dosing of flocculants.

Coagulants are generally polymers with a high cationic charge density toneutralize negative charges of colloids and initiate the formation offlocs. They generally exhibit a relatively low molecular weight in orderto permit a good diffusion of the charges around the particles and a lowviscosity to allow a good distribution of the polymer in the effluents.

By coagulant, one intends to denote a polymer, comprising at least onerepeat unit containing at least one 2-hydroxypropyldialkylammoniumgroup.

An example of a coagulant molecule is presented in FIG. 8.

2.2. Co-Reactants

In the application according to the invention, the product containingepichlorohydrin is usually subjected to a reaction with ammonia, anamine, a polyaminoamide or a polyimine.

The amine can be a mono-, a di- or a polyamine. The amine can bealiphatic, alicyclic or aromatic, saturated or unsaturated, linear orsubstituted. The amine has preferably at least one, more preferably atleast two primary amino hydrogens.

The amine can be represented by the general formula:

H—(NH—R²¹)_(r)—NR²²—(R²³—NH)_(s)—R²⁴  (XIV)

wherein R²² and R²⁴ can be equal, except when equal to H, or differentand can independently be selected from H, alkyl or alkenyl radical,linear, branched or carbocyclic, having from 1 to 30 carbon atoms, R²¹and R²³ can be equal or different, preferably equal, divalent aliphaticradical aromatic radicals having from 2 to 12 carbon atoms, each of rand s is an integer of from 0 to 6, r plus s equals 0 to 6.

Amines include lower alkyl and lower alkenyl primary monoamines, such asmethylamine, ethylamine, isopropylamine, tertbutylamine, mixedamylamines, n-octylamine, branched-chain nonylamine, secondary aminessuch as dimethylamine, ethylmethylamine, diethylamine,propylmethylamine, propylethylamine, dipropylamine, dibutylamine,propylbutylamine, ethylbutylamine, methylbutylamine, pentylethylamine,pentylethylamine, and pentylpropylamine, tertiary amines, as well asalkylenediamines, triamines and polyamines, with or without an alkenylor alkyl substituent bonded to nitrogen, such as ethylenediamine,propylenediamine, butylenediamine, pentylenediamine, hexylenediamine,octylenediamine, dodecylenediamine, cyclohexylenediamine,diethylenetriamine, dipropylenetriamine, dipentylenetriamine,triethylene tetramine, tributylenetetramine, trihexylenetetramine,tetraethylenepentamine, tetrapropylenepentamine, pentahexylenehexamine,pentapropylenehexamine, N-ethyl-1,2-ethylenediamine,N-(2-propenyl)-1,3-propanediamine, N-hexyl-1,4-butanediamine,N-2ethylhexyl-1,3-propanediamine, N-(5-octenyl)-1,6-hexanediamine,N-butyltriethylenetriamine, N-hexyltripropylenetetramine,N-nonyltetrabutylenepentamine and N-(oleyl)-heaxethyleneheptamine,N-alkyl-1,3-diaminopropane, butane and hexane, where the radical alkylcan be hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, and tetracosyl.

The monoamine is preferably a secondary amine, more preferablydimethylamine.

The diamine is more preferably selected from 1,2-diaminoethane,1,2-diaminopropane, 1,3-diaminopropane, a N-substituted diaminopropane,more preferably, 1-amino-3-dimethylaminopropane,1-amino-3-diethylaminopropane, 1-amino-3-cyclohexylaminopropane,N,N,N′,N′-tetramethyl-1,3-propanediamine, 1,3-diaminobutane,1,5-diaminopentane, 1,8-diaminooctane, 1,10-diaminodecane,1,12-diaminododecane, 2-(diethylamino)ethylamine,1-diethylamino-4-aminopentane,3-aminomethyl-3,5,5-trimethylcyclohexylamine andN,N,N′,N′,-tetramethyl-1,6-hexanediamine.

Polyaminoamides are generally obtained from polyamide, preferablypolyacrylamide, formaldehyde and an amine, preferably a secondary amine.Poly[N-(dialkylaminoalkyl)acrylamide] is particularly preferred.

Polyimines are usually obtained by ring opening polymerization ofalkylene imine, preferably ethylene imine.

2.3. Processes

The reaction between the product containing epichlorohydrin and thecompound containing at least one, preferably two primary amino hydrogenscan be carried out by any process known in the art.

The reaction is generally carried out in the liquid phase, possibly inthe presence of a solvent. The solvent may be selected from water, anorganic solvent, preferably miscible with water, or mixtures thereof.Water is preferred. Monoalcohols, like methanol, ethanol, n-propanol,isopropanol and butanol are preferred organic solvents

When a solvent is used, the ammonia or amine content in thesolvent-ammonia or amine mixture is usually higher than or equal to 5%by weight (% wt), preferably higher than or equal to 10 wt %, morepreferably higher than or equal to 20 wt % and most preferably higherthan or equal to 45 wt %. That content is usually lower than or equal to90 wt %, preferably lower than or equal to 75 wt %, more preferablylower than or equal to 60 wt %, and most preferably lower than or equalto 55 wt %.

The molar ratio between epichlorohydrin and ammonia or amine isgenerally higher than or equal to 0.1, preferably higher than or equalto 0.5, more preferably higher than or equal to 0.75 and most preferablyhigher than or equal to 1. That ratio is usually lower than or equal to10, preferably lower than or equal to 5, more preferably lower than orequal to 3, and most preferably lower than or equal to 2.

The temperature at which the reaction is carried out is generally higherthan or equal to 10° C., preferably higher than or equal to 25° C., morepreferably higher than or equal to 50° C. and most preferably higherthan or equal to 60° C. That temperature is usually lower than or equalto 120° C., preferably lower than or equal to 110° C., more preferablylower than or equal to 100° C., and most preferably lower than or equalto 90° C.

The pressure at which the reaction is carried out is generally higherthan or equal to 0.1 bar absolute, preferably higher than or equal to0.2 bar, more preferably higher than or equal to 0.5 bar and mostpreferably higher than or equal to 1 bar. That pressure is usually lowerthan or equal to 20 bar, preferably lower than or equal to 10 bar, morepreferably lower than or equal to 5 bar, and most preferably lower thanor equal to 2 bar.

The duration of the reaction is generally higher than or equal to 10 minabsolute, preferably higher than or equal to 20 min, more preferablyhigher than or equal to 30 min and most preferably higher than or equalto 60 min. That duration is usually lower than or equal to 10 h,preferably lower than or equal to h, more preferably lower than or equalto 3 h, and most preferably lower than or equal to 2 h.

The manufacturing procedure usually involves the dissolution of theamines or ammonia in the solvent, followed by a slow addition of theepichlorohydrin, itself possibly dissolved in a solvent, possiblycooling in order to keep the temperature of the reaction between 10 and50° C., often between 25 and 40° C., then after the epichlorohydrinaddition is complete, raising the temperature to between 60 and 90° C.

The reaction product can be recovered as an aqueous solution, or a solidafter further treatments, e.g. distillation of the solvents undervacuum, treatment of the solution with an acid or a base.

These reactions lead to the formation of the monomer. For example areaction between epichlorohydrin and dimethylamine produces theepichlorohydrin dimethylamine monomer. This is then homopolymerized tothe corresponding quaternary ammonium compound which is a low molecularweight cationic polymer used as a coagulant. Such polymerization usuallytakes place under alkaline conditions.

The monomer can also be copolymerized with acrylamide to produce highermolecular weight polymers also used for water treatment.

2.4. Products Characteristics

The obtained polymers usually exhibit a molecular weight that is higherthan or equal to 5 000, often higher than or equal to 10 000, andfrequently higher than or equal to 50 000. That molecular weight isusually lower than or equal to 500 000, often lower than or equal to 400000, and frequently lower than or equal to 300 000. They can be obtainedas aqueous solution containing from to 50% by weight of polymers andexhibiting viscosities from 40 to 11 000 centipoise.

2.5. Uses

These polymers can be used for treatment of raw water for conversion todrinking water, for recycling paper of water in Pulp & Paper Industry,for paint detackification, for breaking oil emulsions, for oil andgrease removal, and for sludge dewatering. They can also be used forsugar refining.

3. Products for Food-Drink Applications—Wet-Strength Resins 3.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of products that will be used in applicationswhere they will come in contact with food and drink, more specificallyfor the manufacture of wet-strength resins.

By wet-strength resin one intends to denote a polyaminoamide polymer,the chemical formula of which contains at least one group selected from2,3-epoxypropylamine, 2,3-epoxypropylammonium,3-chloro-2-hydroxypropylamine, 3-chloro-2-hydroxypropylammonium,3-hydroxyazetidinium, and any combination of at least two of them.

Examples of chemical formulas of such a polymer are presented in FIG. 9.

3.2. Co-Reactants

In the application according to the invention, the product containingepichlorohydrin is usually subjected to a reaction with a polyamine or apolyamide.

The polyamine and the reactions conditions are as described above forthe manufacture of coagulants.

The polyamide is usually obtained by reacting an amine, preferably apolyalkylene polyamine (in this case the polyamide is generally referredas a polyaminamide) and a dicarboxylic acid, preferably a saturatedaliphatic dicarboxylic acid, as described in U.S. Pat. No. 865,727, thecontent of which is incorporated herein by reference. The polyamide maybe represented by the general formula

—NH—(R²¹)_(r)—NR²²—(R²³—NH)_(s)—COR²⁴CO—  (XV)

where R²¹, R²², R²³, r and s are as described above, and R²⁴ is thedivalent hydrocarbon radical of the dibasic carboxylic acid, preferablyselected from phenylene, naphthalene, methylene, ethylene, propylene,butylenes, pentylene, hexylene, octylene and nonylene.

Preferably, the polyamide may be represented by the general formula

—NH(C_(t)H_(2t)HN)_(x)—COR²⁴CO—  (XVI)

wherein t and x are each 2 or more and whereinthe —NH(C_(t)H_(2t)HN)_(x)— group is derived from the polyaminesdescribed above, preferably containing from 2 to 8 alkylene groups, morepreferably from diethylenetriamine, triethylenetetramine,tetraethylenepentamine, dipropylenetriamine andN-bis(aminopropyl)methylaminethe —COR²⁴CO— group is derived from dibasic carboxylic acid containingfrom 2 to 12 carbon atoms, preferably selected from phenylene,naphthalene, methylene, ethylene, propylene, butylenes, pentylene,hexylene, octylene and nonylene. The acid is more preferably selectedfrom malonic, succinic, glutaric, adipic, diglycolic, sebacic or azelaicacid, and mixtures thereof.

3.3. Processes

The reaction between the polyamide and epichlorohydrin is usuallycarried out at a temperature generally higher than or equal to 45° C.That temperature is usually lower than or equal to 100° C., preferablylower than or equal to 70° C. The temperature at which the reaction isconducted is preferably selected in two stages. In the first stage, thereaction mixture is maintained at 30° C.-50° C., preferably 39°-41° C.Reaction time for the first stage is preferably about 90-190 minutes toform an intermediate polyaminochlorohydrin. Then the reactiontemperature is gradually increased to 55°-75° C. such that theintermediate polyaminochlorohydrin is controllably cross-linked to adetermined level. The second stage is continued until the viscosity ofthe reaction mixture reaches the desired level (preferably level M to Non a Gardner-Holdt viscosity scale).

Broadly speaking, the reaction can be carried out neat or in an aqueoussolution of up to 57 wt % in water. Preferably, the polyaminoamide isreacted with epichlorohydrin in an aqueous solution of 52-57 wt % inwater that is, a solution of 43-48 wt % total solids (the weightpercentage of the solution that is solubilized solid material), morepreferably about 45 wt % total solids. Reaction time varies depending onthe temperature, with lower temperatures taking longer times. Thetypical composition of these resins is 12.5% (10-40% solids). However,due to the cost of transporting water, companies have tried to produceresin solutions of higher concentration. It appears that at least one ofthe main issues making such concentrated solutions difficult to prepareis their high content of dichloropropanol so the level of this impurityis exceeded in the final application.

Reaction is preferably carried out until all, or substantially all ofthe available amine groups on the polyaminoamide are reacted withepichlorohydrin. Generally, reaction times vary between about 1 and 19hours, preferably between 3 and 6 hours. Because the reaction isexothermic, the epichlorohydrin is added slowly over time to thepolyaminoamide to allow for more effective heat transfer from thereaction medium. Heat transfer from the reaction medium can beaccomplished according to known procedures, such as immersing thereaction vessel in a refrigerated environment, e.g., an ice bath, orpassing refrigerated coils inside the reaction vessel.

The reaction is usually carried out in aqueous solution to moderate thereaction. The pH adjustment is usually not necessary but since the pHdecreases during the reaction, it may be desirable in some cases, to addalkali to combine with at least some of the acid formed.

In the reaction, it is preferred to use sufficient epichlorohydrin toconvert the entire secondary amine group to tertiary amine groups. Themolar ratio between epichlorhydrin and the secondary amine groups isusually higher than or equal to 0.1, preferably higher than or equal to0.5, and more preferably higher than or equal to 1. That molar ratio isusually lower than or equal to 10, preferably lower than or equal to 5,and more preferably lower than or equal to 2.

The reaction between the polyamide and epichlorohydrin can also becarried in the presence of a quaternizing agent, the conditions ofreaction and the reactants, except for the inclusion of the quaternizingagent, being essentially the same as described above. In a preferredprocedure, the epichlorhydrin is first added to an aqueous solution ofthe polyamide at a temperature from 45 to 55° C. The reaction mixture isthen heated to a temperature from about 60 to 100° C., and preferablyfrom about 50 to 80° C., depending on the rate of the polymerizationdesired. After a suitable time at that temperature, i.e., 0 to 100 min,a time after which the epoxy group of the epichlorohydrin have reactedwith the secondary amine groups of the polyamide, the quaternizing agentis added and the reaction mixture heated, preferably at a temperaturefrom 60° C. to 80° C. The pH of the reaction mixture is then reduced to4, preferably between 2 and 3 with any suitable acid such as sulphuric,hydrochloric formic and the like. The amount of quaternizing agentshould be sufficient to convert from 25% to 75%, preferably 50% of thetertiary amine group to quaternary group.

The quaternizing agent may be any compound capable of quaternizing atertiary nitrogen atom in an aqueous medium. In general these compoundsare characterized by having as a principal part of their structure analkyl group or substituted alkyl group which is readily available foralkylation under the conditions herein described. These include thelower alkyl esters of mineral acids such the halides, sulfates andphosphates, and substituted alkyl halides. Illustrative of thesecompounds which may be used are dimethyl, diethyl and dipropylsulfate,methyl chloride, methyl iodide, methyl bromide, ethyl bromide, propylbromide, the mono-, di- or tri-methyl, ethyl and propyl phosphates,1,3-dcihloropropanol-2 and 1-chloroglycerol. Certain aromatic compoundsmay also be used like benzyl chloride and methyl p-toluene sulfonate.

The above products resulting from the reaction between epichlorohydrinand the polyamide can be further cross polymerized by treatment with asodium carbonate or sodium hydroxide solution at a pH between 10.5 and12.

3.4. Uses

These resins are used in papers that will get wet such as paper towels,tea bags, coffee filters, milk cartons, meat wrapping, wallpaper. Theycan also be used in the production of high fructose corn syrup and toprevent wool from shrinking.

4. Cationization Agents 4.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of cationization agents.

By cationization agent, one intends to denote a quaternary ammoniumsalt, the chemical formula of which contains at least one group selectedfrom 2,3-epoxypropyl, 3-chloro-2-hydroxypropyl, and their combination,and which is not a polymer.

Cationization agents are often quaternary ammonium salt containing aglycidyl or a 3-chloro-2-hydroxypropyl group attached to the nitrogenatom. The cationization agent can be isolated as solids or as solutionin water or in organic solvents.

Examples of cationization agents are 3-chloro-2-hydroxypropyltrimethylammonium chloride and glycidyl trimethyl ammonium chloride.

4.2. Co-Reactants

In the application according to the invention, the product containingepichlorohydrin is usually subjected to a reaction with an amine, anamine salt, or a mixture thereof.

The amine is preferably a tertiary amine and the amine salt ispreferably a tertiary amine salt.

The tertiary amine salt is for instance a salt obtained by treating anamine with an acid, preferably an inorganic acid, like for instancehydrochloric or sulphuric acid.

The tertiary amine may be represented by the formula

R³¹—N(R³²)—R³³  (XVII)

wherein R³¹, R³² and R³³ can be selected from the group consisting ofalkyl, cycloalkyl, alkene, aryl, aralkyl, alkylaryl, two of them beingpossibly joined to form a ring and containing from 1 to 25 carbon atoms.The group attached to the nitrogen can be linear or substituted,saturated or unsaturated.

If all three of R³¹, R³² and R³³ are the same, they preferably eachshould not contain more than 4 carbon atoms. If all three of R³¹, R³²and R³³ are not the same and if R³³ contains up to 18 carbon atoms, theR³¹ and R³² should preferably be of the group consisting of methyl andethyl. If R³¹ and R³² are joined to form a ring, then R³³ shouldpreferably be from the group consisting of methyl and ethyl.

Examples of suitable tertiary amines are triethylamine, N-methyl andN-ethylmorpholine, N-ethyl and N-methylpiperidine and methyldiallylamine, trimethylamine, dimethylbenzylamine, dimethyldodecylamine,dimethylstearylamines, dimethylaniline, tri-npropylamine.

It is particularly preferred that the tertiary amine possess two methylgroups attached to the nitrogen, like for instance, trimethylamine,dimethylbenzylamine, dimethyldodecylamine, dimethylstearylamine, anddimethylaniline.

The amine salt is preferably a salt obtained by reaction between theabove described amines with hydrochloric or sulfuric acid, preferablywith hydrochloric acid.

4.3. Processes

The reaction between the product containing epichlorohydrin and theamine or the amine salt can be carried out by any process known in theart such as those described in U.S. Pat. No. 2,876,217 the content ofwhich is incorporated herein by reference.

The reaction is generally carried out in the liquid phase, possibly inthe presence of a solvent. The solvent may be selected from water, anorganic solvent e.g. an alcohol, a ketone, an ester or an aliphatichydrocarbon, preferably miscible with water, or mixtures thereof. Wateris preferred. Monoalcohols, like methanol, ethanol, n-propanol,isopropanol and butanol are preferred organic solvents, with methanolbeing particularly preferred.

The content of epichlorohydrin in the solvent is usually higher than orequal to 0.1 mol/l, often higher than or equal to 0.5 mol/l, frequentlyhigher than or equal to 1.0 mol/l, particularly higher than or equal to2 mol/l, specifically higher than or equal to 5 mol/l and sometimeshigher than or equal to 10 mol/l. That epichlorohydrin content isusually lower than 20 mol/l.

The content of amine or amine salt in the solvent is usually higher thanor equal to 0.1 mol/l, often higher than or equal to 0.5 mol/l,frequently higher than or equal to 1.0 mol/l, particularly higher thanor equal to 2 mol/l, specifically higher than or equal to 5 mol/l andsometimes higher than or equal to 10 mol/l. That amine or amine saltcontent is usually lower than 20 mol/l.

The molar epichlorohydrine/amine or amine salt ratio is usually higherthan or equal to 0.1, preferably higher than or equal to 0.5, morepreferably higher than or equal to 1 and most preferably higher than orequal to 1.2. That ratio is usually lower than or equal to 10, morepreferably lower than or equal to and lost preferably lower than orequal to 2.

The temperature at which the reaction is carried out is generally higherthan or equal to 0° C., preferably higher than or equal to 10° C., morepreferably higher than or equal to 25° C. and most preferably higherthan or equal to 40° C. That temperature is usually lower than or equalto 100° C., preferably lower than or equal to 80° C., more preferablylower than or equal to 60° C., and most preferably lower than or equalto 50° C.

The pressure at which the reaction is carried out is generally higherthan or equal to 0.1 bar absolute, preferably higher than or equal to0.2 bar, more preferably higher than or equal to 0.5 bar and mostpreferably higher than or equal to 1 bar. That pressure is usually lowerthan or equal to 20 bar, preferably lower than or equal to 10 bar, morepreferably lower than or equal to 5 bar, and most preferably lower thanor equal to 2 bar.

The duration of the reaction is generally higher than or equal to 10 minabsolute, preferably higher than or equal to 20 min, more preferablyhigher than or equal to 30 min and most preferably higher than or equalto 60 min. That duration is usually lower than or equal to 72 h,preferably lower than or equal to 60 h, more preferably lower than orequal to 48 h, and most preferably lower than or equal to 10 h.

When an amine salt or a mixture of an amine and of an amine salt isused, the pH of the reaction is usually at least 5, and preferably atleast 6. That pH is usually at most 9, preferably at most 8.

In a first embodiment, the manufacturing procedure usually involves themixing of the amine, epichlorohydrin and water, followed by heating atthe desired temperature for the desired duration. The aqueous solutionis further concentrated by vacuum distillation. The temperature ofdistillation is as described for the reaction. The distillation pressureis usually lower than or equal to 100 mbar absolute, preferably lowerthan or equal to 75 mbar and most preferably lower than or equal to 50mbar. That pressure is usually higher than or equal to 1 mbar absolute.

In a second embodiment, an aqueous solution of the amine is first addedto hydrochloric acid until a pH between 8 and 9 is obtained.Epichlorohydrin is further added to the resulting solution and themixture stirred at the desired temperature for the desired duration. Thesolution is further distilled under vacuum to the solid3-chloro-2-trialkylammonium chloride. The solid can be used as such orfurther cyclized into the glycidyl derivative by reaction with sodiumhydroxide in aqueous solution.

In a third embodiment, an amine hydrochloride is dispersed in water.Sufficient sodium hydroxide is added to raise de pH from around 3 toaround 8. Epichlorohydrin is further added to the resulting solution andthe mixture stirred at the desired temperature for the desired duration.The chlorohydrin group is further cyclized into the glycidyl derivativeby reaction with sodium hydroxide in aqueous solution.

In the various embodiments, the aqueous solution obtained at the end ofthe reaction can be further concentrated by vacuum evaporation ordistillation at a temperature of less than 50° C. in order to obtain aslurry containing at least 90% by weight of solid, preferably at least95% by weight. A water miscible alcohol having 3 to 4 carbon atoms, suchas isopropanol, n-propanol, and tert-butanol, preferably isopropanol, isadded to the slurry, such as to obtain an alcohol content from 10 to 70%wt, preferably from 25 to 50% wt, based on the total weight of theresulting alcohol-water slurry. The precipitated solids are thenrecovered by filtration or by other means suitable for removing solidsfrom liquid. The solid may optionally be washed with additional volumesof alcohol or another non-solvent and/or dried to remove any trace ofwater and alcohol.

The reaction product can be recovered as an aqueous solution, or a solidafter further treatments, e.g. distillation of the solvents undervacuum, treatment of the solution with an acid or a base.

4.4. Uses

Cationization agents are mainly used in the cationization of starch tobe utilized by the paper industry for processing of high quality papergrades or for cationization of textile for dye fixing.

5. Flame Retardants 5.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of flame retardants additives.

The product containing epichlorohydrin according to the invention canpreferably be used for the manufacture of phosphorus containing flameretardants additives.

By phosphorus containing flame retardants, one intends to denote acompound, the chemical formula of which contains at least one phosphorusatom and at least one group selected from 2,3-epoxypropyloxy,3-chloro-2-hydroxypropyl, and the combination of at least two of them.

Examples of chemical formulas for such compounds are presented in FIG.10.

5.2. Co-Reactants

In the application according to the invention, the product containingepichlorohydrin is usually subjected to a reaction with an inorganic ororganic compound containing phosphorus. Such inorganic compounds are forinstance a phosphoric acid (ortho, pyro and polyphosphoric acid), aphosphoric acid salt and a phosphorus oxychloride. Examples of organiccompounds containing phosphorus are for instance phosphoric acid esters(of ortho, pyro and polyphosphoric acid), phosphonic acids, their estersor their salts, phosphinic acids, their esters or their salts andphosphine oxides.

The compounds containing phosphorus may be represented by the generalformula

O═P(X¹)(X²)(X³)  (XVIII)

or

P(X¹)(X²)(X³)  (XIX)

wherein X¹, X², X³ can independently be selected from a halogen, H, OH,OR⁴¹, R⁴¹, OR⁴²(OH)_(n) and R⁴²(OH)_(n)wherein the halogen is preferably selected from bromine and chlorine andis preferably chlorinewherein R⁴¹ is an alkyl, an aryl, an alkylaryl, an arylalkyl, acycloalkyl radical containing from 1 to 20 carbon atoms, often from 3 to12 carbon atomswherein R⁴² is an alkylene, arylene, alkylarylene, arylalkylene,cycloalkylene radical containing from 1 to 20 carbon atoms, often from 3to 12 carbon atomswherein n is an integer equal to 1 or 2wherein at least two of X¹, X², X³ can be joined to form a ring,preferably with the phosphorus atom.

Examples of phosphorus containing compounds aretris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl)phosphate, tris(2,3-dichloropropyl) phosphate,isobutylbis(hydroxypropyl)phosphine oxide,10-(2′,5′-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DHQEP), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), thereaction products of DOPO and 4,4′-dihydroxybenzophenone (DOPO2OH and2DOPO-PhOH, II as represented in Liu Y. L., Journal of Polymer Science:Part A: Polymer Chemistry, 2002, Vol. 40, 359-368 and Journal of AppliedPolymer Science, 2002, Vol. 83, 1697-1701).

5.3. Processes

The reaction between the product containing epichlorohydrin and thephosphorus containing compound is carried out by any process known inthe art such as those described in Journal of Applied Polymer Science,2002, Vol. 83, 1697-1701).

The reaction is generally carried out in the liquid phase, possibly inthe presence of a solvent. The solvent may be selected from water, anorganic solvent e.g. an alcohol, or mixtures thereof. An alcohol ispreferred. Monoalcohols, like methanol, ethanol, n-propanol, isopropanoland butanol are preferred organic solvents, with ethanol beingparticularly preferred.

The content of epichlorohydrin in the reaction mixture is usually higherthan or equal to 0.1 mol/l, often higher than or equal to 1.0 mol/l,frequently higher than or equal to 2 mol/l and particularly higher thanor equal to 5 mol/l. That epichlorohydrin content is usually lower than20 mol/l.

The content of the phosphorus containing compound in the reactionmixture is usually higher than or equal to 0.1 mol/l, often higher thanor equal to 0.2 mol/l and frequently higher than or equal to 0.5 mol/l.That content is usually lower than 2 mol/l.

The molar epichlorohydrin/phosphorus containing compound ratio isusually higher than or equal to 1, preferably higher than or equal to 2,more preferably higher than or equal to 5 and most preferably higherthan or equal to 10. That ratio is usually lower than or equal to 50,more preferably lower than or equal to 30 and most preferably lower thanor equal to 20.

The temperature at which the reaction is carried out is generally higherthan or equal to 0° C., often higher than or equal to 5° C., frequentlyhigher than or equal to 10° C., particularly higher than or equal to 20°C. and more specifically higher than or equal to 50° C. That temperatureis usually lower than or equal to 100° C., preferably lower than orequal to 80° C., more preferably lower than or equal to 60° C., and mostpreferably lower than or equal to 30° C.

The pressure at which the reaction is carried out is generally higherthan or equal to 0.1 bar absolute, preferably higher than or equal to0.2 bar, more preferably higher than or equal to 0.5 bar and mostpreferably higher than or equal to 1 bar. That pressure is usually lowerthan or equal to 20 bar, preferably lower than or equal to 10 bar, morepreferably lower than or equal to 5 bar, and most preferably lower thanor equal to 2 bar.

The duration of the reaction depends on the temperature at which thereaction is carried out. That duration is generally higher than or equalto 10 min absolute, preferably higher than or equal to 1 h, morepreferably higher than or equal to 10 min and most preferably higherthan or equal to 24 h. That duration is usually lower than or equal to72 h, preferably lower than or equal to 60 h, more preferably lower thanor equal to 48 h, and most preferably lower than or equal to 30 h.

A basic compound, e.g., potassium hydroxide can be present in thereaction medium. This is generally the case when the phosphoruscontaining compound includes OH groups in the molecule. The molar basiccompound/phosphorus containing compound ratio is usually higher than orequal to 0.1, preferably higher than or equal to 0.15, and mostpreferably higher than or equal to 0.2. That ratio is usually lower thanor equal to 5, more preferably lower than or equal to 3 and lostpreferably lower than or equal to 1.

An onium salt, preferably a quaternary ammonium or phosphonium salt,more preferably a quaternary ammonium chloride, like for instancebenzyltrimethylammonium chloride, can be present in the reaction medium.This is generally the case when the phosphorus containing compound is aphosphine oxide. The onium/phosphorus containing compound ratio isusually higher than or equal to 0.01, preferably higher than or equal to0.05, and most preferably higher than or equal to 0.1. That ratio isusually lower than or equal to 1, more preferably lower than or equal to0.5 and most preferably lower than or equal to 0.2.

The product of the reaction can be recovered by any means, e.g.,filtration and submitted to washing operations before being submitted toevaporation under reduced pressure.

5.4. Uses

Flame retardants are usually used to inhibit the evolution ofcombustible gases in various materials such as polymers, in particularin polyurethane foams.

6. Detergent Ingredients 6.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of detergent ingredients. By detergentingredient, one intends to denote a compound, the chemical formula ofwhich contains at least one 3-sulfonate-2-hydroxy-propyloxy group. Thecompound can be an oligomer or a polymer. An oligomer is a polymer witha number of repeat units in each polymer molecule of less than 20.

By detergent ingredient, one intends to denote a polymer, at least onerepeat unit of which comprises at least one 2-hydroxypropylammoniumgroup, preferably a 2-hydroxypropylimidazolidium group.

The product containing epichlorohydrin according to the invention canpreferably be used for the manufacture of cationic monomers, polymers oroligomers, anionic surfactants, for instance sulfonates basedsurfactants, preferably alkyl glyceryl ether sulfonate surfactants,monomeric or oligomeric or cationic cyclic amine based polymers.

6.2. Co-Reactants

In the application according to the invention, when the detergentauxiliary is a sulfonate based surfactant, the product containingepichlorohydrin is usually subjected to a reaction with an aliphaticalcohol containing from 10 to 40 carbon atoms, preferably from 10 to 22carbon atoms more preferably from 14 to 18 carbon atoms and mostpreferably from 16 to 18 carbon atoms. The alkyl chain may be branchedor linear or ethoxylated, wherein when present, the branches comprise analkyl moiety containing from 1 to 4 carbon atoms, such as methyl orethyl.

In the application according to the invention, when the detergentingredient is a cationic amine based polymer, the product containingepichlorohydrin is usually subjected to a reaction with an amineselected from the group consisting of linear alkylamines, branchedalkylamines, cycloalkylamines, alkoxyamines, amino alcohols, cyclicamines containing at least one nitrogen atom in a ring structure,alkylenediamines, polyetherdiamines, polyalkylenepolyaminesamine.

Specific examples of the said amines are given above.

Cyclic amines containing at least one nitrogen atom in a ring structureare for example monoaminoalkylpiperazines, bis(aminoalkyl)piperazines,monoaminoalkylimidazoles, aminoalkylmorpholines, aminoalkylpiperidinesand aminoalkylpyrrolidines. The monoaminoalkylpiperazines are forexample 1-(2-aminoethyl)piperazine and 1-(3-aminopropyl)piperazine.Preferred monoaminoalkylimidazoles have 2 to 8 carbon atoms in the alkylgroup. Examples of suitable compounds are 1-(2-aminoethyl)imidazole and1-(3-aminopropyl)imidazole. Suitable bis(aminoalkyl)piperazines are forexample 1,4-bis(2-aminoethyl)piperazine and1,4-bis(3-aminopropyl)-piperazine. Preferred aminoalkylmorpholines areaminoethylmorpholine and 4-(3-aminopropyl)-morpholine. Other preferredcompounds of this group are aminoethylpiperidine, aminopropylpiperidineand aminopropylpyrrolidine.

Cyclic amines with at least two reactive nitrogen atoms in the ring arefor example imidazole, C-alkyl substituted imidazoles having 1 to 25carbon atoms in the alkyl group such as 2-methylimidazole,2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole and2-isobutylimidazole, imidazoline, C-alkyl substituted imidazolineshaving 1 to 25 carbon atoms in the alkyl group and arylimidazolines suchas 2-phenylimidazoline and 2-tolylimidazoline, piperazine,N-alkylpiperazines having 1 to 25 carbon atoms in the alkyl group suchas 1-ethylpiperazine, 1-(2-hydroxy-1-ethyl)piperazine,1-(2-hydroxy-1-propyl)piperazine, 1-(2-hydroxy-1-butyl)piperazine,1-(2-hydroxy-1-pentyl)piperazine, 1-(2,3-dihydroxy-1-propyl)piperazine,1-(2-hydroxy-3-phenoxyethyl)piperazine,1-(2-hydroxy-2-phenyl-1-ethyl)piperazine,

N,N′-dialkylpiperazines having 1 to 25 carbon atoms in the alkyl groupfor example 1,4-dimethylpiperazine, 1,4-diethylpiperazine,1,4-dipropylpiperazine, 1,4-dibenzylpiperazine,1,4-bis(2-hydroxy-1-ethyl)piperazine,1,4-bis(2-hydroxy-1-propyl)piperazine,1,4-bis(2-hydroxy-1-butyl)piperazine,1,4-bis(2-hydroxy-1-pentyl)piperazine, and1,4-bis(2-hydroxy-2-phenyl-1-ethyl)piperazine. Other cyclic amines withat least two reactive nitrogen atoms are melamine and benzimidazolessuch as 2-hydroxybenzimidazole and 2-aminobenzimidazole.

6.3. Processes

The reaction between the product containing epichlorohydrin and thealcohol is carried out by any process known in the art such as thosedescribed in U.S. Pat. No. 5,567,359 and US 2006/0079433, the contentsof which are incorporated herein by reference.

The reaction is usually carried out at a temperature between 65 and 90°C.

Typical molar ratios of alcohol:epichlorohydrin range from 1:1.24 to1:4.02.

A catalyst is usually used when carrying out the reaction, for instancestannic chloride. The mass ratio of initial alcohol:stannic chloride isgenerally of 100:0.67.

The duration of the reaction is usually between 0.25 and 1 h.

The epichlorohydrin/alcohol ratio and the duration can be adapted to therequired degree of oligomerisation

Epichlorhydrin is usually slowly added to the alcohol-catalyst mixture.

The product of the reaction is a monomeric or oligomeric alkylchloroglyceryl ether.

The alkyl chloroglyceryl ether is further converted into an alkylglycidyl ether by reaction with a basic compound, preferably sodiumhydroxide. That reaction is usually carried out with a 35% aqueoussolution of sodium hydroxide at a temperature higher than 90° C. and fora molar ratio alcohol:NaOH of 1:1.5.

The alkyl glycidyl ether is further converted into an alkyl glycerylsurfactant by reaction usually with a mixture of sodium bisulfite andsodium sulfite, generally obtained by combining sodium meta-bisulfitewith sodium hydroxide.

The reaction between the product containing epichlorohydrin and theamine is carried out by any process known in the art such as thosedescribed in U.S. Pat. No. 6,740,633 and US 2006/0052272, the contentsof which are incorporated herein by reference.

The reaction is usually carried out at a temperature between 25 and 90°C., in two steps the first one at a temperature between 40 and 60° C.and the second one between 90 and 100° C.

Typical molar ratios of amine:epichlorohydrin range from 1: to 1:1.4.

The duration of the reaction is usually between 0.25 and 1 h.

The condensation product between the amine and epichlorohydrin isusually further quaternarized using alkyl halides, epoxides,chloroacetic acid, 2-chloroethanesulfonic acid, chloropropionic acid,epoxysuccinic acid, propane sulfone, 3-chloro-2-hydroxypropanesulfonicacid, dimethyl sulfate and/or diethyl sulfate, or oxidized by oxidationof the tertiary nitrogen atoms of the condensation products to N-oxides.

6.4. Uses

Examples of detergent ingredients are surfactants or surface depositionenhancing materials. They are usually used as components of cleaningcompositions for instance dishwashing, laundry compositions, shampoosand synbars.

7. Epichlorohydrin Elastomers 7.1. General

The product containing epichlorohydrin according to the invention can beused for the manufacture of epichlorohydrin elastomers.

By epichlorohydrin elastomer, one intends to denote a polymer,containing at least one type of repeat units, at least one type ofrepeat units containing at least one 2-chloromethylethoxy group. Thepolymer can a homopolymer or a copolymer.

Examples of epichlorohydrin elastomers are homopolymers ofepichlorohydrin, copolymers of epichlorohydrin with an alkylene orphenylene oxide, and terpolymers of epichlorohydrin with an alkylene orphenylene oxide, and a glycidyl ether.

The alkylene oxide can be selected from styrene oxide, propylene oxide,ethylene oxide, butene-1 oxide, dodecene-1-oxide, and is preferablyethylene oxide.

The glycidyl ether can be selected from alkyl and haloalkyl glycidylethers, for instance, 2-chloroethyl glycidyl ether and allyl glycidylether.

7.2. Co-Reactants

In the application according to the invention, the product containingepichlorohydrin is usually subjected to a reaction with an alkylene orphenylene oxide or with an alkylene or phenylene oxide and a glycidylether or the epichlorohydrin is homopolymerized.

7.3. Processes

The reaction is carried out by any process known in the art such asthose described in U.S. Pat. No. 3,135,705, U.S. Pat. No. 3,158,580,U.S. Pat. No. 3,158,581, U.S. Pat. No. 3,026,270 and U.S. Pat. No.3,341,491, the contents of which are incorporated herein by reference.

The reaction is usually carried out in solution in aliphatic or aromatichydrocarbons, chlorinated hydrocarbons, or ether.

The weight ratio between epichlorhydrin and the alkylene oxide isusually between 20:80 and 90:10.

The reaction is preferably carried out in the presence of a catalystformed by reacting R⁵¹ ₃Al and water (thought to be R⁵¹ ₂Al—O—AlR⁵¹ ₂),where R⁵¹ can be selected from alkyl, cycloalkyl, aryl or alkarylradical. The catalyst activity can be improved by the addition ofacetylacetone. Some combinations of organozinc and organomagnesiumcompounds, as well as other additives and chelating agents incombination with alkylaluminum compounds, are also effective catalysts.

The reaction can be carried out in a continuous process using aback-mixed reactor.

The temperature at which the reaction can be carried out is usuallycomprised between −80° C. and 250° C., preferably between −80 and 150°C., more preferably between −30 and 100° C. A temperature between 25 and50° C. is particularly convenient

The homopolymer of epichlorohydrin and the copolymers can be furthercross-linked, e.g, by further reacting with a polyamine, or an amine inthe presence of at least one agent from the group of sulfur,dithiocarbamates, thiuram sulfides and thiazoles, or with a metalcompound selected from the group consisting of salts of aromaticcarboxylic acids, aliphatic carboxylic acids, carbonic acid, phosphorousacid, silicic acid, and oxides of the metals of Groups IIA, IIB and IVAof the periodic Table and at least one heterocyclic compound selectedfrom the group consisting of 2-mercaptoimidazolines and2-mercaptopyrimidine.

7.4. Uses

The epichlorohydrin elastomers are generally used in specialtyapplications, like for instance automotive components (fuel pumpdiaphragms, emission control hoses, motor mounts, gaskets, seals andportable fuel tanks), in the aircraft industry, for specialty roofingmembranes, coated fabrics, solvent storage containers, paper mill andprinting roll and in a variety of oil specialties. −80° C. and 250° C.,preferably between −80 and 150° C., more preferably between −30 and 100°C. A temperature between 25 and 50° C. is particularly convenient

The homopolymer of epichlorohydrin and the copolymers can be furthercross-linked, e.g, by further reacting with a polyamine, or an amine inthe presence of at least one agent from the group of sulfur,dithiocarbamates, thiuram sulfides.

A further goal of the invention is to provide epichlorohydrin which canbe used in various applications, obtained from a starting materialdifferent from propylene. The invention therefore further relates to theuse of epichlorohydrin obtained from glycerol in the manufacture ofglycidyl amides or glycidyl imides or coagulants or wet-strength resinsor cationization agents or flame retardants, or detergent ingredients.

EXAMPLES

Five epichlorohydrin (ECH) samples have been used. Their compositionsobtained by gas chromatography analysis are presented in Table 1.

TABLE 1 Component (g/kg) ECH 1 ECH 2 ECH3 ECH4 ECH5 acetaldehyde 0.004n.d n.d n.d. n.d. acrolein <0.001 0.003 0.003 n.d. n.d. 2-propanol<0.001 n.d. n.d. n.d. n.d. 3-chloro-1-propene n.d. n.d. n.d. n.d. n.d.allyl alcohol 0.001 <0.001 <0.001 n.d. 0.003 hydroxyacetone 0.094 0.0180.018 0.006 0.006 chloroacetone + (3,3- 0.033 0.038 0.040 n.d. 0.024dichloro-1-propene) 1,2-dichloropropane 0.042 n.d. n.d. 0.001 n.d.2,3-dichloro-1-propene 0.005 n.d. n.d. 0.004 n.d.1-chloro-2,3- >998.464 >999.474 >999.045 >999.503 >999.865 epoxypropane(*) 1,3-dichloro-1-propene 0.219 0.008 0.008 0.032 0.004 cis maj. +(C6H14O min.) 2-chloro-2-propene-1-ol 0.348 0.016 0.016 0.14 0.0121,3-dichloro-1-propene 0.035 0.010 0.010 0.008 0.009 transC₅H₁₀O/C₄H₇ClO n.d. n.d. n.d. 0.014 0.001 C₆H₁₂O n.d. n.d. n.d. 0.011<0.001 1,3-dichloropropane 0.002 0.34 0.34 0.005 0.030 Cyclopentanone0.001 0.004 0.004 n.d. 0.004 dibromochloromethane 0.004 n.d. n.d. 0.084n.d. C₆H₁₀O iso 1 0.003 n.d. n.d. 0.009 <0.001 C₆H₁₀O iso 2 0.012 n.d.n.d. 0.009 0.001 1,2-epoxyhexane + 0.030 0.002 0.002 n.d. 0.001(1,2,2-trichloropropane) C₆H₁₀O iso 3 0.004 n.d. n.d. 0.031 0.001dichloroepoxypropane 0.003 n.d. n.d. 0.006 n.d.1,3,3-trichloro-1-propene 0.012 n.d. n.d. 0.004 n.d. cis + 1,1,3-trichloropropene 1,1,2-trichloropropane 0.211 0.001 0.001 0.025 0.007chlorobenzene 0.011 <0.001 <0.001 0.001 0.007 1,3,3-trichloro-1-propene0.015 n.d. n.d. 0.012 0.001 trans 1,2,3-trichloropropene 0.016 <0.001<0.001 0.003 0.001 trans 1,3-dichloro-2-propanol 0.111 0.023 0.024 0.0170.008 1,2,3-trichloropropane 0.014 n.d. n.d. 0.024 n.d.1,2,3-trichloropropene cis 0.002 n.d. n.d. n.d. n.d.3-chloro-1,2-propanediol + 0.13 <0.001 0.001 n.d. 0.0012,3-dichloro-1-propanol C₆H₁₃Br n.d. n.d. n.d. 0.005 n.d. C₆H₁₀Cl₂ iso 1n.d. n.d. n.d. 0.005 n.d. C₆H₁₀Cl₂ iso 2 n.d. n.d. n.d. 0.004 n.d.methyl glycidyl ether 0.007 0.054 0.48 n.m. n.m. Unknowns (sum) 0.1700.007 0.008 0.087 0.024 n.d.: not detected, n.m.: not measured (*):1-chloro-2,3-epoxypropane amount calculated on the basis of the totalcontent of other organic components

Examples 1 to 10 Homopolymerization of ECH

The tests have been carried out according to the following procedurewith epichlorohydrin sample ECH1 (examples 1 to 3), ECH 2 (examples 4 to6) and ECH 3 (examples 7 to 10). The quantities of chemicals areindicated in Table 2.

The polymerization of epichlorohydrin (ECH) has been carried out in thepresence of the system tetraoctylammonium bromide(Noct₄Br)/triisobutylaluminium (TiBA).

The epichlorohydrin has been dried over calcium hydride under vacuum for24 h at 25° C. and further distilled.

The polymerization reactions have been carried out in pyrex vesselsfitted with polytetrafluorethylene valves. The vessels have beenevacuated under flame heating to remove residual moisture. After coolingto room temperature, the vessels have been cooled to −30° C.(ethanol/liquid nitrogen cooling bath) and toluene and epichlorohydrin,have been added under vacuum. After those additions, argon has beenintroduced in the vessel and tetraoctylammonium bromide and triisobutylaluminium have been added to the vessel. This addition constituted thetime zero of the reaction. After a given time under magnetic stirring at−30° C., the reaction has been stopped by adding 1-2 ml of ethanol tothe vessel. Half of the volume of the reaction medium has then beensubmitted to evaporation after which the polymer has been recovered fromthe vessel.

The conversion has been obtained by comparing the weight of recoveredpolymer with the weight of added epichlorohydrin.

The theoretical molar weight (Mn th.) has been calculated on the basisof the quantity of tetraoctylammonium bromide.

The measured polymer molar weight (Mn exp) and the molar weightdispersion have been obtained by Gel Permeation Chromatography.

The tacticity of the polymer has been obtained by ¹³C and ¹H NMR.

The results of the tests are summarized in Table 3.

TABLE 2 Example n^(o) ECH (ml) Toluene (ml) Noct₄Br (ml) TiBA (ml) 1 410.2 2.15 0.71 2 4 10.2 2.15 0.71 3 3.4 9.9 0.91 0.30 4 4 10.2 2.15 0.715 4 10.2 2.15 0.71 6 4 11.6 1.08 0.35 7 4 10.2 2.15 0.71 8 4 10.2 2.150.71 9 3.6 11.4 0.97 0.43 10 4 11.6 1.08 0.35

TABLE 3 Reaction Conversion Mn th. Mn exp. Example time (h) (mol %)(g/mol) (g/mol) Dispersion Tacticity 1 1 100 10000 10700 1.17 atactic 21 100 10000 10100 1.23 n.m. 3 2 100 20000 20200 1.17 n.m. 4 1 100 1000016400 1.22 n.m. 5 1 100 10000 11200 1.20 atactic 6 1 100 20000 77700(20%) 1.40 n.m. 22200 (80%) 1.20 7 1 80 8000  6800 1.17 n.m. 8 2 95 950012100 1.17 atactic 9 2 90 18000 24700 1.18 n.m. 10 6 94 18800 17650 1.17n.m. n.m.: not measured

Examples 13 to 15 Homopolymerization of ECH

The tests have been carried out according to the following procedurewith epichlorohydrin sample ECH1 (example 13), ECH 2 (example 14) andECH 3 (example 15). The quantities of chemicals are indicated in Table4.

The polymerization of epichlorohydrin (ECH) has been carried out in thepresence of the system water/triethyl aluminium (TEA).

The procedure of example 1 has been followed except that TEA in solutionin toluene and water have been added under argon to the vessel firstevacuated and dried, left under magnetic stirring under vacuum for 30min, before ECH in toluene has been added (time zero of the reaction).The polymerization has been carried out at a temperature of 25° C. for12 h. The results have been summarized in Table 5

TABLE 4 Example n^(o) ECH (ml) Toluene (ml) H₂0 (μl) TEA (ml) 13 4 10 230.67 14 4 10 23 0.67 15 4 10 23 0.67

TABLE 5 Reaction Conversion Mn exp. Example time (h) (mol %) (g/mol)Dispersion Tacticity 13 12 47 216000 2.02 n.m. 7000 1.04 14 12 50 2852003.51 atactic 5850 1.08 15 12 55 357600 3.45 atactic 8100 1.31 n.m.: notmeasured

Example 16

Preparation of a product consisting predominantly in diglycidyl dietherof Bisphenol A according to U.S. Pat. No. 2,811,227

The apparatus employed was a thermostatised flask equipped with amechanical stirrer, with a jacket containing a thermocouple and with aDean-Stark separator surmounted by a water-cooled condenser. A pump wasused to inject a caustic soda aqueous solution at a constant rate in theflask.

The reaction flask was initially charged with a mixture of bisphenol A(68.4 g, 0.3 mol) and the epichlorohydrin sample ECH4 coming from apropylene-chlorine plant (277.5 g, 3.0 mol). The analysis of theepichlorydrin is given in Table 1. The trichloropropane content is of0.049 g/kg. The mixture was heated at reflux under stirring to atemperature of 111° C. A 40% aqueous solution of caustic soda (60.8 g,0.6 mol) was introduced at a rate of 12 ml/h during 3.5 hour. Thetemperature of the mixture in the flask was maintained in the range 100°C.-115° C. in order to assure a constant reflux. The epichlorohydrinrich organic phase decanted during the reaction as a lower phase in theseparator was recycled regularly in the reaction flask and the aqueousrich phase collected as an upper phase in the separator was regularlydrawn off. The heating was maintained for 15 min after the totalintroduction of the caustic soda solution to achieve the collect of thewater phase in the decantor. 29.7 g of aqueous phase was collected witha composition given in Table 6.

The epichlorohydrin in excess was removed from the reaction mixture bydistillation under a vacuum of 30 mbar and by a progressive heating ofthe mixture to 109° C. 156.1 g (1.7 mol) of epichlorohydrin wasrecovered in this step. The composition of the distillate is given inTable 6.

The salt was separated from the crude product (45.5 g) after addition of567.2 g of toluene under agitation and by filtration. The cake offiltration was washed with 124.4 g of toluene. The toluene solutionswere mixed and evaporated at 185° C. under a pressure of 1 mbar.

659.4 g of toluene was recovered as the condensate of the evaporatedfraction with a composition given in Table 6. The residual product ofthe evaporation (100.5 g) contained the diglycidyl ether of bis-phenol Aas a major product and no trace of unconverted bis-phenol A (<5 mg/kg).The residue contained 4.98 mol epoxy per kg and 1.52% of hydrolysablechlorine.

Example 17

The trial was realized in the apparatus described in example 16.

The reaction flask was initially charged with a mixture of bisphenol A(68.4 g, 0.3 mol) and epichlorohydrin sample ECH 5 (277.5 g, 3.0 mol).The analysis of the epichlorydrin is given in Table 1. Thetrichloropropane content is of 0.007 g/kg. The mixture was heated atreflux under stirring to a temperature of 119° C. A 40% aqueous solutionof caustic soda (60.8 g, 0.6 mol) was introduced at a rate of 12 ml/hduring 3.5 hour. The temperature of the mixture in the flask wasmaintained in the range 102° C.-119° C. in order to assure a constantreflux. The epichlorohydrin rich organic phase decanted during thereaction as a lower phase in the separator was recycled regularly in thereaction flask and the aqueous rich phase collected as an upper phase inthe separator was regularly drawn off. The heating was maintained for 15min after the total introduction of the caustic soda solution to achievethe collect of the water phase in the decantor. 54.5 g of aqueous phasewas collected with a composition given in Table 6.

The epichlorohydrin in excess was removed from the reaction mixture bydistillation under a vacuum of 30 mbar and by a progressive heating ofthe mixture to 118° C. 148.2 g (1.5 mol) of epichlorohydrin wasrecovered in this step. The composition of the distillate is given inTable 6.

The salt was separated from the crude product (47.8 g) after addition of228.4 g of toluene under agitation and by filtration. The cake offiltration was washed with 97.3 g of toluene. The toluene solutions weremixed and evaporated at 180° C. under a pressure of 1 mbar.

305.0 g of toluene was recovered as the condensate of the evaporationwith a composition given in Table 6. The residual product of theevaporation (99.8 g) contained the diglycidyl ether of bis-phenol A as amajor product and no trace of unconverted bis-phenol A (<5 mg/kg). Theresidue contained 4.93 mol epoxy per kg and 0.49% of hydrolysablechlorine.

The High Performance Liquid Chromatography analyses of the residualproducts obtained in examples 16 and 17 are similar.

TABLE 6 Example 16 Example 17 Water Toluene Water TolueneEpichlorohydrin evaporated evaporated Epichlorohydrin evaporatedevaporated Component evaporated (g/kg) (mg/l) (g/kg) evaporated (g/kg)(mg/l) (g/kg) acetaldehyde n.d. 2.9 n.d. n.d. 1.3 n.d. acrolein n.d.0.58 n.d. 0.002 0.42 n.d. 2-propanol n.d. <0.05 n.d. n.d. 0.3 n.d.3-chloro-1-propene 0.001 n.d. n.d. n.d. n.d. n.d. allyl alcohol n.d.n.d. n.d. 0.001 0.2 n.d. hydroxyacetone 0.016 n.d. n.d. 0.002 n.d. n.d.chloroacetone + (3,3-dichloro-1- 0.003 0.65 n.d. 0.002 0.53 n.d.propene) 1,2-dichloropropane n.d. n.d. n.d. n.d. 2,3-dichloro-1-propene0.005 0.07 n.d. n.d. n.d. n.d. 1-chloro-2,3-epoxypropane principalproduct (45 g/kg) 1.6  principal product (46 g/kg) 3.3 1,3-dichloro-1-propene cis maj. + 0.026 0.36 n.d. 0.003 n.d. n.d.(C6H14O min.) 2-chloro-2-propene-1-ol 0.19  0.12 n.d. 0.016 <0.05 n.d.1,3-dichloro-1-propene trans 0.007 <0.05 n.d. 0.008 n.d. n.d.C₅H₁₀O/C₄H₇ClO 0.019 0.05 n.d. 0.001 n.d. n.d. C₆H₁₂O 0.022 0.28 n.d.0.021 n.d. n.d. 1,3-dichloropropane 0.001 n.d. n.d. 0.03  <0.05 n.d.Cyclopentanone n.d. n.d. n.d. 0.006 n.d. n.d. dibromochloromethane 0.080n.d. n.d. n.d. n.d. n.d. C₆H₁₀O iso 1 0.033 0.11 n.d. 0.038 n.d. n.d.C₆H₁₀O iso 2 0.040 0.31 n.d. 0.001 n.d. n.d. 1,2-epoxyhexane + (1,2,2-n.d. n.d. n.d. 0.001 n.d. n.d. trichloropropane) C₆H₁₀O iso 3 0.036 0.21n.d. 0.002 n.d. n.d. dichloroepoxypropane 0.006 n.d. n.d. n.d. n.d. n.d.1,3,3-trichloro-1-propene cis + 1,1,3- 0.006 n.d. n.d. n.d. n.d. n.d.trichloropropene 1,1,2-trichloropropane 0.005 n.d. n.d. n.d. n.d.chlorobenzene 0.001 n.d. n.d. 0.008 n.d. n.d. 1,3,3-trichloro-1-propenetrans 0.009 n.d. n.d. n.d. n.d. n.d. 1,2,3-trichloropropene trans 0.003n.d. n.d. 0.001 n.d. n.d. 1,3-dichloro-2-propanol 3.4  143 0.38  2.5 111 0.074 1,2,3-trichloropropane 0.022 n.d. 0.002 n.d. n.d. n.d.1,2,3-trichloropropene cis n.d. n.d. n.d. n.d. n.d. n.d.3-chloro-1,2-propanediol + 2,3- 0.13  5.9 0.064 0.071 4.1 0.033dichloro-1-propanol C₆H₁₃Br n.d. <0.05 0.005 n.d. <0.05 C₆H₁₀Cl₂ iso 10.009 n.d. n.d. n.d. n.d. n.d. C₆H₁₀Cl₂ iso 2 0.007 n.d. n.d. n.d. n.d.n.d. methyl glycidyl ether n.m. n.m. n.m. n.m. n.m. n.m. Unknowns (sum)0.299 10.00 1.31  0.213 1.3 1.373 n.d.: not detected, n.m.: not measured

Example 18

A glass thermostated jacketed reactor having a working volume of 305 mlwas supplied continuously with 47.2 wt % sodium hydroxide and with anaqueous mixture of dichloropropanol, a mixture prepared from glyceroland concentrated hydrochloric acid in the presence of an organic acidaccording to the International Application WO 2005/054167 filed bySolvay SA. The mixture contained 575 g of water/kg, 404.6 g of1,3-dichloro-2-propanol/kg, 20.1 g of 2,3-dichloro-1-propanol/kg, 0.14 gof acrolein/kg, 0.13 g of epichlorohydrin/kg, 0.04 g of1,2,3-trichloropropane/kg, 0.04 g of chloroacetone/kg and 0.03 g of anether of crude formula C₆H₁₀O₂Cl₂/kg. The sodium hydroxide wasintroduced at a flow rate of 262 g/h and the aqueous dichloropropanolmixture was introduced at a flow rate of 1180 g/h. The reaction mediumwas constantly maintained at 25° C. with vigorous stirring. The liquidmixture exiting the reactor by continuous overflow was collected andthen separated in batch mode in a glass funnel so as to obtain a firstseparated fraction and a second separated fraction. 3753 g of firstseparated fraction (MEL1) were subjected to a batch distillation under avacuum of 193 mbar. The batch distillation was carried out using around-bottomed flask equipped with a magnetic stirrer bar, athermocouple to measure the temperature of the liquid and a platedistillation column surmounted by a device enabling part of thedistillate to be refluxed at the top of the column. The glass platecolumn comprised 5 plates having a diameter of 30 mm, pierced by aninternal aperture 10 mm diameter central hole for the flow of liquid andthree rows of small holes having a diameter of around 0.8 mm, spaced atregular intervals of less than 1 mm between each hole, placed in an arcover three quarters of the circumference. The spacing between the plateswas 30 mm. The column was adiabatic (glass jacket under vacuum). Athermocouple placed in the top of the distillation column enabled thetemperature of the gas phase distilled to be measured. The distillatewas collected in a funnel with a stopcock. A first distillation fractionwas collected between 49° C. and 67° C. and gave, after separation, 425g of an organic phase (D1 org) and 159 g of an aqueous phase (D1 aq).The organic phase (D1 org) was combined with the contents of the boilerto give the mixture (MEL2) which was then distilled at a temperature of187° C. A second distillation fraction was collected between 66° C. and67° C. and resulted, after separation, in 244 g of an organic phase (D2org) and 11.5 g of an aqueous phase (D2 aq). A main distillate of 2082 gof epichlorohydrin at 999.5 g/kg was then collected (D3) at atemperature of 67° C. The mixture constituting the final boiler (MEL3)weighed 1226 g and only contained a very low fraction of epichlorohydrinimplemented. The organic phase D2 org and the boiler MEL3 could berecycled to the distillation operations in order to recover, forenhanced value, epichlorohydrin and a mixture of 1,3-dichloro-2-propanoland 2,3-dichloro-1-propanol respectively. The compositions (g/kg) usedand obtained in the distillation operations are described in Table 7.

TABLE 7 MEL1 D1 org D1 aq MEL2 D2 org D2 aq D3 MEL3 Acrolein 0.2 0.610.13 0.076 0.99 0.12 0.050 0.006 Acetone 0.006 0.024 0.02 <0.005 0.0270.01 <0.01 <0.005 Isopropanol 0.032 0.124 n.d. 0.014 0.15 n.d. <0.005n.d. 2-Chloropropane 0.047 0.021 n.d. <0.005 0.012 n.d. n.d. n.d. Allylalcohol 0.003 n.d. n.d. 0.003 n.d. n.d. n.d. 2,3-Epoxybutane <0.0050.008 n.d. n.d. 0.010 n.d. n.d. n.d. C₄H₈O <0.005 0.010 n.d. n.d. 0.012n.d. n.d. n.d. 2-Butanone <0.005 0.003 n.d. n.d. 0.005 n.d. n.d. n.d.Hydroxyacetone n.d. n.d. n.d. 0.001 n.d. n.d. n.d. Chloroethanol n.d.0.005 n.d. n.d. 0.001 n.d. n.d. n.d. Chloroacetone 0.039 0.025 n.d.0.039 0.034 0.03 0.05 0.019 Epichlorohydrin 653 982 46 666 989 36 999.529 Glycidol 0.06 0.000 n.d. 0.07 n.d. n.d. n.d. 0.242-chloro-2-propen-1-ol <0.005 0.005 0.16 <0.005 0.008 0.04 <0.01 0.005cis-1,3-Dichloropropene n.d. 0.003 0.03 <0.005 0.003 0.02 <0.01 <0.005trans-1,3-Dichloropropene n.d. 0.005 n.d. <0.005 0.009 n.d. <0.01 <0.0051,1,1-Trichloropropane <0.005 n.d. n.d. <0.005 n.d. n.d. n.d. 0.002Cyclopentanone 0.021 n.d. n.d. 0.023 n.d. n.d. <0.01 0.0213-Chloro-1-propanol 0.013 0.000 n.d. 0.020 n.d. n.d. n.d. 0.016cis-1,3,3-Trichloropropene n.d. n.d. n.d. n.d. n.d. n.d. n.d. <0.005C₄H₇ClO₂ n.d. 0.000 n.d. n.d. n.d. n.d. n.d. <0.005 Ethylbenzene <0.0050.000 n.d. n.d. n.d. n.d. n.d. <0.005 1,3-Dichloropropan-2-ol 251 0.3640.27 271 0.013 0.82 0.010 789 2-Methyl-2-cyclopenten-1-one n.d. n.d.n.d. <0.005 n.d. n.d. n.d. <0.005 1,2,3-Trichloropropane 0.16 n.d. n.d.0.018 n.d. n.d. n.d. 0.015 2,3-Dichloro-1-propanol + 3- 56 1.94 36.42 610.046 21 n.d. 174 chloro-1,2-propanediol Phenol 0.011 n.d. n.d. 0.012n.d. n.d. n.d. 0.035 C₆H₈O₂ <0.005 n.d. n.d. <0.005 n.d. n.d. <0.010.008 C₆H₁₂OCl₂ 0.056 n.d. n.d. 0.060 n.d. n.d. n.d. 0.0513,5-Dimethyl-2-cyclohexen-1- 0.011 n.d. n.d. 0.012 n.d. n.d. n.d. 0.035one C₆H₉Cl₃O₂ 0.031 n.d. n.d. 0.034 n.d. n.d. n.d. 0.1021-Phenoxy-2-propanone 0.88 n.d. n.d. 0.078 n.d. n.d. n.d. 1.754C₆H₁₀Cl₂O₂ 0.076 0.002 n.d. 0.101 n.d. n.d. n.d. 0.325 C₉H₉Cl₃ <0.005n.d. n.d. <0.005 n.d. n.d. n.d. 0.012 C₆H₁₁O₂Cl₃ 0.74 n.d. n.d. 0.81n.d. n.d. n.d. 2.95 C₉H₁₅O₂Cl₂ + C₉H₁₇O₄Cl₃ <0.005 n.d. n.d. <0.005 n.d.n.d. n.d. 0.56 Sum of unknowns 0.27 0.07 0.16 0.31 0.08 n.d. n.d. 1.07Methyl glycidyl ether 0.02 n.d. n.d. 0.03 0.03 n.d. 0.04 H₂O 37 14.0n.d. 2.32 9.9 n.d. 0.32 0.33 n.d. = not detected

1. A method for the manufacture of a material selected from the groupconsisting of epoxy resins, glycidyl esters, glycidyl ethers, glycidylamides, glycidyl imides, epichlorohydrin elastomers, coagulants,wet-strength resins, cationization agents, flame retardants anddetergent ingredients comprising subjecting a product comprisingepichlorohydrin and trichloropropane to a reaction in order to obtainsaid material, wherein the product comprises a positive amount oftrichloropropane in an amount of up to less than 0.01 g oftrichloropropane per kg of product.
 2. The method according to claim 1,wherein said method is a method for the manufacture of a materialselected from the group consisting of epoxy resins, glycidyl esters,glycidyl ethers, glycidyl amides, glycidyl imides, and epichlorohydrinelastomers.
 3. The method according to claim 1, wherein said productfurther comprises at least one or more of the following compounds: (A)halogenated hydrocarbon compounds different from trichloropropane chosenfrom chloropropene, trichloropropene, chloropropanol, chloropropenol,dichloropropene, dichloropropane, dichloropropanol,monochloropropanediol, chloroethers, monochlorobenzene, and any mixtureof at least two of them, and/or (B) compounds chosen from acrolein,methyl glycidyl ether, chloroacetone, glycerol, hydroxyacetone,glycidol, cyclopentanone and any mixture of at least two of them.
 4. Themethod according to claim 1, wherein the trichloropropane is chosen from1,2,3-trichloropropane, 1,1,1-trichloropropane, 1,1,3-trichloropropane,1,1,2-trichloropropane and any mixtures of at least two of them.
 5. Themethod according to claim 1, wherein said product comprises more than900 g of epichlorohydrin per kg of product.
 6. The method according toclaim 1, wherein the product is subjected to a reaction with a compoundcontaining at least one active hydrogen atom, selected frommonoalcohols, monocarboxylic acids, polyols, polyamines, amino alcohols,polyimides and amides, polycarboxylic acids, and mixtures thereof, inorder to obtain an epoxy resin or a glycidyl ether or a glycidyl esteror a glycidyl amide or a glycidyl imide.
 7. The method according toclaim 1, wherein the product is reacted with ammonia, an amine, apolyaminoamide or a polyimine in order to obtain a coagulant, or whereinthe product is reacted with a polyamine, a polyamide or a polyaminoamidein order to obtain a wet-strength resin, or wherein the product isreacted with an amine, an amine salt, or a mixture thereof in order toobtain a cationization agent.
 8. The method according to claim 1,wherein the product is reacted with a compound selected from phosphoricacid, a phosphoric acid salt, a phosphorus oxychloride, a phosphoricacid ester, a phosphonic acid, a phosphonic acid ester, a phosphonicacid salt, a phosphinic acid, a phosphinic acid ester, a phosphinic acidsalt, a phosphine oxide, a phosphine, or a mixture thereof, in order toobtain a flame retardant.
 9. The method according to claim 1, whereinthe product is reacted with a monoalcohol containing from 12 to 16carbon atoms or an ethoxylated alcohol or with an amine selected fromthe group consisting of linear alkylamines, branched alkylamines,cycloalkylamines, alkoxyamines, amino alcohols, cyclic amines containingat least one nitrogen atom in a ring structure, alkylenediamines,polyetherdiamines, and polyalkylenepolyamines in order to produce adetergent ingredient.
 10. The method according to claim 1, wherein theproduct containing epichlorohydrin is reacted with an alkylene orphenylene oxide or with an alkylene or phenylene oxide and a glycidylether or homopolymerized in order to obtain an epichlorohydrinelastomer.
 11. The method according to claim 1, wherein the productcomprises trichloropropane in an amount of 0.001 mg/kg to less than 0.01g of trichloropropane per kg of product.
 12. The method according toclaim 1, wherein the product comprises trichloropropane in an amount of0.001 mg/kg to less than or equal to 0.008 g per kg of product.
 13. Themethod according to claim 1, wherein the product comprisestrichloropropane in an amount of 0.001 mg/kg to less than or equal to0.006 g per kg of product.
 14. The method according to claim 1, whereinthe product comprises trichloropropane in an amount of 0.001 mg/kg toless than or equal to 0.004 g per kg of product.
 15. The methodaccording to claim 1, wherein said method is a method for themanufacture of a material selected from the group consisting of epoxyresins and glycidyl ethers.
 16. The method according to claim 1, whereinsaid method is a method for the manufacture of epoxy resins.
 17. Themethod according to claim 1, wherein the product is subjected to areaction with a compound containing at least one active hydrogen atom,selected from polyols, and mixtures thereof, in order to obtain an epoxyresin or a glycidyl ether.
 18. The method according to claim 1, whereinthe product is subjected to a reaction with a compound containing atleast one active hydrogen atom, selected from polyols, and mixturesthereof, in order to obtain an epoxy resin.